KR20130079518A - Toner, method for producing the toner, and image forming method - Google Patents

Abstract

A toner comprising a binder resin containing an ester bond, and a release agent, wherein the release agent comprises a first C30-C50 alkyl monoester compound and a second C30-C50 alkyl monoester compound, wherein the first C30-C50 alkyl mono The number of carbon atoms in the ester compound is different from that of the second C30-C50 alkyl monoester compound, with the highest amount of the first C30-C50 alkyl monoester compound and two amounts of the second C30-C50 alkyl monoester compound Second or the same as the amount of the first C30-C50 alkyl monoester compound, the amount of the first C30-C50 alkyl monoester compound is at least 30% by mass and less than 50% by mass relative to the release agent, the second C30-C50 alkyl The amount of the monoester compound is 10 mass% or more and less than 50 mass% with respect to the mold release agent.

Description

TONER, METHOD FOR PRODUCING THE TONER, AND IMAGE FORMING METHOD}

The present invention relates to a toner, a manufacturing method of the toner, and an image forming method.

For example, the developer used in electrophotographic, electrostatic recording and electrostatic printing is, in the developing step, attached to the image bearing member on which the electrostatic image is formed; Then, in the transferring step, transferred from the image bearing member onto a recording medium (eg, recording paper sheet); In the fixing step, it is fixed to the surface of the recording medium. As is known, these developers for developing an electrostatic image formed on an image bearing member include a two-component developer composed of a carrier and a toner and a one-component developer (magnetic or nonmagnetic toner) that does not require a carrier. It is largely classified.

Conventionally, dry toners used for electrophotographic, electrostatic recording, electrostatic printing and the like have been prepared by finely pulverizing melt-kneaded products of toner binders (for example styrene resins and polyesters) and colorants.

In order to obtain high quality and high resolution images, improvements have been made by making the particle size of the toner particles small. However, toner particles obtained by a commonly used manufacturing method using kneading and grinding are amorphous. Therefore, toner particles due to agitation with a carrier in the developing apparatus, or due to contact stresses with a developing roller, a toner-feeding roller, a layer thickness-adjusting blade, a frictionally charged blade, and the like when the toner is used as a one-component developer, Is further milled to form ultrafine particles; Undesirable phenomena occur in which the image quality is reduced due to the fluidizing agent embedded in the toner surface. In addition, due to their amorphous shape, the fluidity of the toner particles as powder is poor, and a large amount of fluidizing agent is required, and the toner particle filling rate of the toner bottle is low, which hinders miniaturization. Therefore, at present, the advantages of such toner particles having a small particle diameter are not revealed. That is, there is a limit to the particle size that can be made small by the pulverization method, and toner particles having a smaller particle size cannot be produced by this pulverization method. In addition, poor transferability due to the amorphous shape of the pulverized toner particles causes image loss in the transferred image, and requires consumption of a large amount of toner to compensate for this image loss.

In view of this, there is an increasing demand for higher transfer efficiency to obtain high quality images without image loss and to reduce the amount of toner consumed to reduce operating costs. In other words, when the transfer efficiency is quite high, it is not necessary to use a cleaning unit to remove the untransferred toner from the image carrier and the recording medium. As a result, the advantages of miniaturization of the device, cost reduction, and no waste of toner are also obtained.

In order to solve the problems caused by such amorphous shapes, various manufacturing methods of spherical toners have been proposed. However, spherical toner particles expose their surface in all directions from the outside and are in easy contact with the carrier and the charging member, such as the charging blade. As a result, the spherical toner particles have reduced chargeability over time due to contamination, the background portion is stained with the toner, and toner scattering occurs.

As a method for solving these problems, Patent Document 1 includes the steps of dispersing or dissolving a toner material in a volatile solvent such as an organic solvent having a low boiling point; Emulsifying or forming the resulting dispersion or droplets of solution in an aqueous medium in the presence of a dispersant; And removing the volatile solvent to prepare the toner. This proposed technique produces toner by so-called polymer dissolution suspension, which involves volume shrinkage. The volume of the droplets shrinks in the step of removing volatile solvents. As a dispersant, when using a solid particulate dispersant that does not dissolve in an aqueous medium, only amorphous particles are produced, which is problematic. In addition, when the solid content of the solvent is increased to increase the productivity, the viscosity of the dispersion phase is increased, so that the obtained particles have a large particle size and the distribution thereof is wide. In contrast, when the molecular weight of the resin to be used is reduced to decrease the viscosity of the dispersed phase, fixability (particularly, hot offset resistance) is not sufficiently maintained.

Further, Patent Document 2 includes the steps of dissolving or dispersing a toner material in an organic solvent; Emulsifying or dispersing in an aqueous medium to aggregate the resulting mixture; And removing the organic solvent to form the toner, and melting-kneading the toner material; Dissolving or dispersing the melt-kneaded product in an organic solvent; Emulsifying or dispersing the resulting solution or dispersion in an aqueous medium; And removing the organic solvent to form the toner. This proposed technique prevents phase separation of resins, improves dispersibility of toner components, prevents reaggregation and separation of resins in toner particles, and produces toners having suitable chargeability and releaseability. can do. However, this technique does not sufficiently prevent contamination of carriers and charging members such as charged blades.

Patent Document 3 also proposes a method comprising reacting an active hydrogen group-containing prepolymer with a compound having two or more functional groups in a molecule to react with an active hydrogen group in an aqueous medium to form toner particles. This proposed technique promotes emulsification by reducing the viscosity of the dispersed phase by using a low molecular weight resin in a polymer dissolution suspension method, and conducts a polymerization reaction in particles to improve its fixability. However, this proposed technique does not sufficiently consider the contamination of the toner on the charged member or the like. For example, this technique does not control the shape of the particles and does not prevent contamination of carriers and charging members, such as charged blades.

In addition, Patent Document 4 proposes a toner containing a polyester, a colorant, a mold release agent, and a fatty acid amide compound that serves as a fixing aid. This document describes that the toner manufactured by this proposed technique is excellent in low temperature fixability and offset resistance at high temperature, and also prevents contamination on the fixing apparatus and the image. However, it cannot be said that the toner has sufficient characteristics.

In addition, Patent Document 5 discloses ester compounds having the same number of carbon atoms (that is, the most contained ester compound is only one ester in order to improve high temperature offset resistance, low temperature fixability and blocking resistance and obtain good transparency in OHP). It is proposed an electrostatic developing toner comprising a binder resin containing an ester wax containing a compound) in an amount of 50% by mass to 95% by mass. Since the proposed electrostatic developing toner contains a large amount of ester compounds having the same number of carbon atoms, the melting point is sharp and excellent in fixing at a specific temperature. However, this electrostatic developing toner is difficult to respond to changes in the fixing temperature in a device such as an electrophotographic apparatus. In addition, the electrostatic developing toner is difficult to produce with a toner having low temperature fixability. In addition, the electrostatic developing toner is insufficient in terms of transfer efficiency and contamination in the apparatus, which is a problem.

In order to reduce power consumption, the melting temperature of the toner has been lowered. As a result, the release agent used must be completely dissolved at low temperatures. In order to reduce the power consumption, the heat capacity of the heating medium (e.g. roller or belt) is increased to shorten its warm-up time and at the time of fixing the heating medium (e.g. roller or belt) Measures to reduce the surface temperature are effective. However, when the power is turned on, the shorter the preheating time, the larger the temperature change of the heating medium. In addition, maintaining the temperature of the heating medium at a particular low temperature easily results in a greater change in temperature at continuous feeding. Therefore, corresponding to the change of the fixing temperature; That is, it is necessary to have a wide fixing temperature range.

From this point of view, toners having excellent low temperature fixability, wide fixing temperature range, excellent releasability even at high fixing temperature, excellent transfer efficiency, and low contamination in the apparatus; A method for producing this toner; And the demand for providing an image forming method is increasing.

Patent Document 1: Japanese Patent Application Publication (JP-A) No. 07-152202 Patent Document 2: Japanese Patent (JP-B) No. 4284005 Patent Document 3: JP-A No. 11-149179 Patent Document 4: JP-A No. 2010-2901 Patent Document 5: JP-B No. 3287733

The present invention aims to solve the above-mentioned existing problems and achieve the following object. Specifically, the object of the present invention is toner having excellent low temperature fixability, wide fixing temperature range, excellent releasability even at high fixing temperature, excellent transfer efficiency, and low contamination in the apparatus; A method for producing this toner; And an image forming method.

The present inventors have conducted intensive studies to solve the above problems, and have a toner comprising a binder resin and a release agent containing an ester bond, wherein the release agent is a first C30-C50 alkyl monoester compound and a second C30-. A C50 alkyl monoester compound, wherein the number of carbon atoms of the first C30-C50 alkyl monoester compound is different from the number of carbon atoms of the second C30-C50 alkyl monoester compound, and the first C30-C50 alkyl monoester The amount of the compound is the highest and the amount of the second C30-C50 alkyl monoester compound is the second or the same as the amount of the first C30-C50 alkyl monoester compound, the amount of the first C30-C50 alkyl monoester compound is a release agent The amount of the second C30-C50 alkyl monoester compound is 30% by mass or more and less than 50% by mass with respect to the release agent. Toner, had a superior low-temperature fixing performance, and a wide fixing temperature range, the releasing property is excellent even at high fixing temperature, and excellent transfer efficiency, it was found that less contamination in the apparatus. The present invention has been accomplished based on this finding.

The present invention is based on the above findings obtained by the inventors. The solution to the problem is as follows.

<1> binder resin containing an ester bond, and

Release agent

As a toner comprising:

The release agent comprises a first C30-C50 alkyl monoester compound and a second C30-C50 alkyl monoester compound,

The number of carbon atoms of the first C30-C50 alkyl monoester compound is different from the number of carbon atoms of the second C30-C50 alkyl monoester compound,

The amount of the first C30-C50 alkyl monoester compound is the highest among the release agents and the amount of the second C30-C50 alkyl monoester compound is the second highest among the release agents or the same as the amount of the first C30-C50 alkyl monoester compounds,

The amount of the first C30-C50 alkyl monoester compound is 30% by mass or more and less than 50% by mass with respect to the release agent,

The amount of the second C30-C50 alkyl monoester compound is 10% by mass or more and less than 50% by mass with respect to the release agent.

<2> dissolving or dispersing at least one of a release agent, a binder resin containing an ester bond, and a binder resin precursor containing an ester bond in an organic solvent to prepare a toner material liquid,

Emulsifying or dispersing the toner material liquid in an aqueous medium to prepare an emulsion or dispersion; and

Removing the organic solvent from the emulsion or dispersion to form parent particles

A method of manufacturing a toner according to <1>, comprising.

<3> charging the surface of the image carrier;

Exposing the surface of the charged image bearing to form an electrostatic latent image on the image bearing,

Developing a latent electrostatic image formed on the image carrier with a developer containing toner to form a toner image on the image carrier;

Transferring the toner image onto a recording medium, and

Fixing the transferred toner image onto a recording medium

An image forming method comprising

And the toner is a toner according to < 1 >.

The present invention provides a toner having excellent low temperature fixability, a wide fixing temperature range, excellent releasability even at high fixing temperature, excellent transfer efficiency, and low contamination in the apparatus; A method for producing this toner; And an image forming method. These can solve the above-mentioned existing problems.

1 is a schematic configuration diagram of an exemplary image forming apparatus for implementing the image forming method of the present invention.

(toner)

The toner of the present invention contains at least a binder resin containing an ester bond (ester bond containing binder resin) and a release agent and, if necessary, further contains other components.

It is preferable that the toner contains matrix particles.

<Release Agent>

The release agent contains a first C30-C50 alkyl monoester compound and a second C30-C50 alkyl monoester compound, wherein the number of carbon atoms of the first C30-C50 alkyl monoester compound is equal to that of the second C30-C50 alkyl monoester compound. Different from the number of carbon atoms, the amount of the first C30-C50 alkyl monoester compound is the highest among the release agents and the amount of the second C30-C50 alkyl monoester compound is the second highest among the release agents or the first C30-C50 alkyl monoester Equal to the amount of the compound. The release agent preferably contains a third C30-C50 alkyl monoester compound and, if necessary, further contains other components.

Alkyl monoester compounds are prepared, for example, via esterification reactions between long chain aliphatic carboxylic acid components and long chain aliphatic alcohol components. For example, a relatively high purity long chain aliphatic carboxylic acid (e.g., its alkyl group has about 15 to about 30 carbon atoms) and a high purity long chain aliphatic alcohol (e.g., about 16 to about its alkyl group) Esterification between 35 carbon atoms) provides a mixture of alkyl monoester compounds with a narrow distribution of carbon atoms. Mixtures of alkyl monoester compounds with a narrow distribution of carbon atoms have a narrow melting point and low viscosity. This mixture contains a small amount of components that evaporate at low temperatures and is easily separated from toner particles when heated, so that the releasability is excellent.

In addition, two or more alkyl monoester compounds contained in a predetermined amount in the release agent have suitably different polarities depending on the total number of carbon atoms of the alkyl groups in their molecules. Thus, one component of the alkyl monoester compounds is present near the surface layer of the toner particles to ensure release property at low temperatures. On the other hand, other components of the alkyl monoester compounds are present inside the toner particles (i.e., near the center of the toner particles) and can be released when the toner particles are heated to a high temperature. Such distributed alkyl monoester compounds may exhibit release properties upon settling over a wide temperature range. In addition, because not all components of the release agent are present in the surface layer of the toner particles, the release agent less contaminates the members, such as the charged members (eg, charged blades) and the carrier. Therefore, the use of the toner of the present invention realizes image formation excellent in durability.

In addition, when the toner particles contain the mother particles produced by emulsifying oil droplets in an aqueous medium, the polarity of the alkyl monoester compound greatly affects the state in which the release agent is contained (disposed) in the toner particles. Here, since alkyl monoester compounds having different carbon atoms are mixed together, their polar distribution can be made to suitably contain (dispose) the release agent in the toner particles.

As a result of the researches of the present inventors, alkyl monoester compounds having a relatively low total carbon number tend to exist close to the surface of the toner particles, whereas alkyl monoester compounds having a relatively high total carbon number tend to form inside the toner particles (near the center of the toner particles). And tends to be dispersed).

First and second C30-C50 alkyl monoester compounds

The first C30-C50 alkyl monoester compound is a component of the release agent and is contained in the highest amount.

The second C30-C50 alkyl monoester compound is another component of the release agent and is contained in the second highest amount or in an amount equal to the amount of the first C30-C50 alkyl monoester compound.

The first C30-C50 alkyl monoester compound and the second C30-C50 alkyl monoester compound are not particularly limited and may be appropriately selected depending on the intended purpose. Examples are compounds represented by the following formula (I):

Ra-COO-Rb... (I)

In the above formula, Ra represents a C15-C30 alkyl group, and Rb represents a C1-C34 alkyl group.

Further examples of alkyl monoester compounds contained in the release agent include ester compounds synthesized via esterification reactions between monofunctional long chain aliphatic carboxylic acids and monofunctional long chain aliphatic alcohols.

Examples of monofunctional long-chain aliphatic carboxylic acids include nonadecanoic acid, eicosanoic acid, henicoic acid, docoic acid, tetracoic acid, pentacoic acid, hexacoic acid, heptacoic acid, octacoic acid, nonacoic acid, triacone Carbonic acid, myristic acid, palmitic acid, stearic acid, arachidonic acid and behenic acid, with stearic acid, behenic acid and myristic acid being preferred.

Examples of monofunctional long chain aliphatic alcohols include methanol, ethanol, propanol, butan-1-ol, pentan-1-ol, hexane-1-ol, heptane-1-ol, octane-1-ol, nonan-1-ol, Decan-1-ol, eicosan-1-ol (ecosanol), myristyl alcohol, cetyl alcohol, palmityl alcohol, stearyl alcohol, arachidel alcohol and behenyl alcohol, stearyl alcohol, eicosanol and cetyl Alcohol is preferred.

In the alkyl monoester compound, for example, Ra is preferably a C15-C30 straight chain alkyl group (long chain aliphatic group), more preferably a C17-C21 straight chain alkyl group (long chain aliphatic group). In addition, Rb is preferably a C14-C34 straight chain alkyl group (long chain aliphatic group), and more preferably a C14-C20 straight chain alkyl group (long chain aliphatic group).

It is preferable that the quantity of a 1st C30-C50 alkyl monoester compound is 30 mass% or more and less than 50 mass% with respect to a mold release agent, and is 40 mass% or more and less than 50 mass%. When the amount is less than 30 mass%, the formed toner has a narrow fixing temperature range, and releasability is lowered at a high fixing temperature. In addition, the transfer efficiency of the toner decreases, causing contamination in the apparatus. On the other hand, when the amount is 50% by mass or more, the formed toner has low releasability at high fixing temperature. In addition, the transfer efficiency of the toner decreases, causing contamination in the paper.

It is preferable that the quantity of a 2nd C30-C50 alkyl monoester compound is 10 mass% or more and less than 50 mass% with respect to a mold release agent, and is 40 mass% or more and less than 50 mass%. If the amount is less than 10% by mass, the formed toner cannot cope with a change in the fixing temperature in the apparatus, and the releasability at the upper and lower limits of the temperature in the apparatus is not sufficient.

The difference in the number of carbon atoms between the first C30-C50 alkyl monoester compound and the second C30-C50 alkyl monoester compound is preferably 1 to 12, more preferably 2 to 8, and 4 to 8 absolute. Particularly preferred. If the difference in the number of carbon atoms between them is 13 or more, the increased amount of components evaporate over a certain settling temperature range, potentially causing contamination in the device. When the difference in the number of carbon atoms between them falls within the above particularly preferred range, the formed toner is all excellent in the lowest fixing temperature, fixing temperature range, release property at high fixing temperature, transfer efficiency and contamination resistance in the apparatus, which is useful.

In addition, the fixing temperature in the device is controlled within a specific temperature range (e.g., a narrow temperature range of set temperature ± 10 ° C), so that the number of carbon atoms of the first C30-C50 alkyl monoester compound is equal to the second C30-C50 alkyl monoester If it is 13 or less than that of the compound, the amount of release agent evaporated within the controlled temperature range can be increased (most of the first C30-C50 alkyl monoester compounds are evaporated).

The total amount of the first C30-C50 alkyl monoester compound and the second C30-C50 alkyl monoester compound is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferable that the total amount is 60 mass% or more with respect to a mold release agent, It is more preferable that it is 80 mass% or more, It is especially preferable that it is 90 mass% or more. If the total amount falls within the above particularly preferable range, it is advantageous in that the formed toner has a predetermined release property and causes less contamination in the apparatus.

As for the combination of the first C30-C50 alkyl monoester compound and the second C30-C50 alkyl monoester compound, the combination of the C36 alkyl monoester compound and the C38 alkyl monoester compound, the C36 alkyl monoester compound and the C40 alkyl monoester compound , C36 alkyl monoester compound and C42 alkyl monoester compound, C38 alkyl monoester compound and C42 alkyl monoester compound, C34 alkyl monoester compound and C42 alkyl monoester compound, and C30 alkyl monoester compound And a combination of a C40 alkyl monoester compound is preferred.

Third C30-C50 Alkyl Monoester Compound

The third C30-C50 alkyl monoester compound is a component of the component of the release agent and is contained in the third highest amount or in an amount equal to the amount of the second C30-C50 alkyl monoester compound.

The third C30-C50 alkyl monoester compound is, for example, a compound represented by the general formula (I).

The total amount of the first C30-C50 alkyl monoester compound, the second C30-C50 alkyl monoester compound, and the third C30-C50 alkyl monoester compound is not particularly limited and may be appropriately selected depending on the intended purpose. The total amount is preferably 95 mass% or more with respect to the release agent because the toner to be formed has a predetermined release property and causes less contamination in the apparatus.

The release agent contains, as a main component, a first C30-C50 alkyl monoester compound and a second C30-C50 alkyl monoester compound. Here, other types of release agents (e.g., paraffin) may be contained as long as fixability / release property, low contamination on the charging member, and durability of the formed toner are maintained at a sufficient level.

The release agent may be selected from the group consisting of esterification between starting materials (alcohol and acid) having a different carbon atom number to obtain a predetermined carbon atom number distribution; And through purification. Alternatively, high purity alcohols and acids (starting materials) can be reacted together to synthesize various kinds of alkyl monoester compounds, which can then be mixed together.

The method for obtaining a predetermined release agent by mixing includes, for example, a second C30-C50 mixture of an alkyl monoester compound containing the first C30-C50 alkyl monoester compound as a main component (preferably in an amount of 85% by mass or more). A method of mixing with another alkyl monoester compound mixture containing an alkyl monoester compound (preferably in an amount of at least 85% by mass).

The melting point of the release agent is not particularly limited and may be appropriately selected depending on the desired purpose. It is preferable that it is 50 degreeC-100 degreeC, and it is more preferable that it is 50 degreeC-75 degreeC. If the melting point is less than 50 ° C, blocking easily occurs during storage of the toner, and as a result, the heat resistance storage resistance of the toner may deteriorate. On the other hand, when its melting point is higher than 100 ° C, the low temperature fixability of the toner may decrease.

Here, the melting point refers to the endothermic peak temperature at which the endothermic amount of the sample (toner) is maximized in the differential scanning calorimetry analysis curve obtained through differential scanning calorimetry (DSC) (this temperature is referred to as the "maximum endothermic peak temperature"). .

The melt viscosity of the release agent is not particularly limited and may be appropriately selected depending on the predetermined purpose. 1.0 mPa * sec-20 mPa * sec are preferable, and, as for the melt viscosity in 100 degreeC, 1.0 mPa * sec-10 mPa * sec are more preferable. If the melt viscosity is less than 1.0 mPa · sec, the fluidity of the toner may decrease. On the other hand, when the melt viscosity is more than 20 mPa · sec, the release agent may be insufficiently dispersed in the toner.

Here, melt viscosity can be measured with a Brookfield Rotational Viscometer.

The acid value of the mold release agent is not particularly limited and may be appropriately selected depending on the predetermined purpose. It is preferably 0.1 mgKOH / g to 20 mgKOH / g. In view of the offset resistance and dispersibility of the release agent, the acid value thereof is more preferably 3 mgKOH / g to 15 mgKOH / g. When the acid value is less than 0.1 mgKOH / g, the dispersibility of the release agent may be insufficient, and various properties of the formed toner, such as contamination resistance, may be lowered. On the other hand, when the acid value is more than 20 mgKOH / g, the release agent is easily transferred to the aqueous medium (aqueous phase) in which the toner material liquid (oil phase) is emulsified or dispersed. As a result, the amount of the releasing agent contained in the parent particles of the toner becomes insufficient, so that the offset resistance of the produced toner can be lowered. In addition, since the release agent is easily localized on the surface of the parent particles of the toner, the resulting toner containing the parent particles easily adheres to the developing apparatus, potentially causing image defects. In addition, the separability between the release agent and the polyester is reduced, so that the offset resistance of the formed toner may be lowered.

Here, an acid value can be measured using the potentiometric automatic titrator DL-53 (Mettler-Toledo K.K. product), the electrode DG113-SC (Mettler-Toledo K.K. product), and the analysis software LabX Light Version 1.00.000. The titrator is calibrated with a solvent mixture of toluene (120 mL) and ethanol (30 mL). The measurement temperature is set to 23 ° C. The measurement conditions are as follows.

<Measurement Conditions>

 Stir

  Speed [%] 25

  Time [s] 15

 EQP titration

  Titrant / Sensor

   Titrant CH3ONa

   Concentration [mol / L] 0.1

   Sensor DG115

   Unit of measurement mV

  Predispensing to volume

   Volume [mL] 1.0

   Wait time [s] 0

  Titrant addition Dynamic

   dE (set) [mV] 8.0

   dV (min) [mL] 0.03

   dV (max) [mL] 0.5

  Measure mode Equilibrium controlled

   dE [mV] 0.5

   dt [s] 1.0

   t (min) [s] 2.0

   t (max) [s] 20.0

  Recognition

   Threshold 100.0

   Steepest jump only no

   Range no

   Tendency None

  Termination

   at maximum volume [mL] 10.0

   at potential No

   at slope No

   after number EQPs Yes

    n = 1

   comb. termination conditions No

  Evaluation

   Procedure Standard

   Potential 1 No

   Potential 2 No

   Stop for reevaluation no

Specifically, the acid value is measured as follows according to JIS K0070-1992. First, a sample (0.5 g) is added to toluene (120 mL) and then dissolved for about 10 hours at room temperature (23 ° C.) under stirring. Ethanol (30 mL) is then added to the resulting solution to prepare a sample solution. The sample solution thus prepared was then titrated with a pre-standardized 0.1 N potassium hydroxide alcohol solution to obtain the appropriate amount X (mL). The titrant X thus obtained was used in the following formula to calculate the acid value:

Acid value = X × N × 56.1 / mass of sample [mgKOH / g]

Where N is the factor of 0.1 N potassium hydroxide alcohol solution.

The content of the release agent is not particularly limited and may be appropriately selected depending on the predetermined purpose. It is preferable that the quantity of a mold release agent is 1 mass%-20 mass% with respect to a mother particle. If the amount is less than 1% by mass, the fixing temperature range can be narrowed. On the other hand, if the amount is more than 20% by mass, the transfer efficiency may decrease.

It is preferable that a mold release agent is disperse | distributed finely to a mother particle, without being unevenly distributed on the surface of a mother particle. It is preferable that it is 0.06 micrometer-0.80 micrometer, and, as for the dispersion diameter of a mold release agent, it is more preferable that it is 0.10 micrometer-0.30 micrometer. If its dispersion diameter is more than 0.80 mu m, the amount change of the release agent between the parent particles becomes large, potentially lowering the chargeability and fluidity. Also, a release agent may be attached to the developing apparatus. As a result, high quality images cannot be obtained in some cases. On the other hand, if the dispersion diameter of the release agent is less than 0.06 μm, the proportion of the release agent present in the parent particle becomes high (relatively lower than the proportion of the release agent present on the surface of the parent particle), and potentially the release property is lowered.

Here, the dispersion diameter refers to the maximum diameter of the dispersed particles of the release agent.

In addition, the method of measuring the dispersion diameter of a mold release agent is not specifically limited, For example, it may be the following method.

First, the parent particles are embedded in an epoxy resin, and then the product is sectioned to a thickness of about 100 nm. The fragment thus obtained is stained with ruthenium tetraoxide, and then observed 10,000 times in a transmission electron microscope (TEM), and then photographed. The obtained photograph can be evaluated about the dispersion state of a mold release agent, and the dispersion diameter of a mold release agent can be measured.

<Ester bond containing binder resin>

The ester bond-containing binder resin is not particularly limited and may be appropriately selected depending on the predetermined purpose. An example is polyester.

Examples of polyesters are unmodified polyesters, modified polyesters and crystalline polyesters.

Unmodified polyester refers to a polyester that does not contain other bonding units (eg urethane bonds and urea bonds) in addition to ester bonds.

Modified polyester refers to a polyester containing a bond other than an ester bond.

As the ester bond-containing binder resin, unmodified polyester and modified polyester can be used in combination. For example, unmodified polyester (ii) and modified polyester (i) [eg, urea-modified polyester] can be used as the toner binder component. When using (i) and (ii) together, low temperature fixability improves, and when used in a full color image forming apparatus, gloss also improves. Therefore, it is more preferable to use (i) and (ii) together than to use (i) alone. In addition, it is preferable that (i) and (ii) are mutually compatible at least partially from a viewpoint of low temperature fixability and the improvement of offset resistance. Therefore, the polyester component of (i) is preferably similar to that of (ii).

Unmodified Polyester

The peak molecular weight of the unmodified polyester (ii) is not particularly limited and may be appropriately selected depending on the predetermined purpose. It is generally 1,000 to 30,000, more preferably 1,500 to 10,000, still more preferably 2,000 to 8,000. When the peak molecular weight is less than 1,500, heat preservation resistance may be lowered. On the other hand, when the peak molecular weight is more than 10,000, low temperature fixability may be lowered.

The weight average molecular weight of the unmodified polyester (ii) is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferable that it is 2,000-90,000.

The glass transition temperature (Tg) of the unmodified polyester (ii) is not particularly limited and may be appropriately selected depending on the predetermined purpose. From the standpoint of obtaining a wide range of fixation temperatures, this is preferably from 40 ° C to 80 ° C, more preferably from 50 ° C to 60 ° C.

The hydroxyl value of the unmodified polyester (ii) is not particularly limited and may be appropriately selected depending on the predetermined purpose. It is preferably at least 5 mgKOH / g, more preferably 10 mgKOH / g to 120 mgKOH / g, even more preferably 20 mgKOH / g to 80 mgKOH / g. When the hydroxyl value thereof is less than 5 mgKOH / g, it may be difficult to obtain both the predetermined heat retention and the predetermined low temperature fixability.

The acid value of the unmodified polyester (ii) is not particularly limited and may be appropriately selected depending on the predetermined purpose. It is generally 1 mgKOH / g to 50 mgKOH / g, preferably 5 mgKOH / g to 40 mgKOH / g, more preferably 20 mgKOH / g to 40 mgKOH / g, 30 mgKOH / g to 40 mgKOH / g is particularly preferred. If the acid value falls within the above particularly preferable range, it is advantageous in that the formed toner shows better transferability and generates less contamination in the apparatus. This is likely due to the increased dispersibility of the release agent, which significantly reduces the amount of release agent exposed to the toner surface. When the unmodified polyester has an acid value, the toner formed tends to be negatively charged.

When the acid value and hydroxyl value exceed the above ranges, the toner formed is adversely affected by environmental factors under high temperature, high humidity or low temperature, low humidity environment, and easily causes image defects.

Crystalline Polyester

When the toner contains crystalline polyester together with the modified polyester, various specific alkyl monoester compounds used as release agents are finely dispersed in the toner to prevent contamination of the release agent on the carrier and the charging member. It has also been found that controlling the melt viscosity at 100 ° C. of the alkyl monoester compound greatly contributes to the fine dispersion of the release agent in the toner.

The mechanism by which the crystalline polyester improves the fine dispersion of the alkyl monoester compound is not clear, but the following mechanism is inferred.

Specifically, the crystalline polyester and the alkyl monoester compound are dispersed in the crystalline state without being dissolved in the amorphous resin in the mother particles. Crystalline polyesters have an affinity for alkyl monoester compounds and thus are readily accessible and promote their mutual dispersibility, so that the release agent can be finely dispersed in the parent particles.

In particular, when the mixture of alkyl monoester compounds contains components with different total carbon atoms, one of the components has a high affinity for the crystalline polyester (one component may be a component with more carbon atoms), Still other components have a high affinity for the amorphous polyester component (other components may be component (s) with less carbon atoms). Due to these effects, when properly combined together, the release agent (many alkyl monoester compounds) is sufficiently dispersed in the binder resin (toner binder).

Crystalline polyesters are inherently used to improve fixability. However, in the present invention, the crystalline polyester is contained in the toner material together with an alkyl monoester compound (particularly, an alkyl monoester compound having a melt viscosity of 1.0 mPa sec to 20 mPa sec at 100 ° C, respectively). The use of crystalline polyesters allows the release agent to be finely dispersed in the parent particles, with the result that the amount of release agent exposed to the surface of the parent particles is reduced; That is, the release agent is not ubiquitous on its surface, and the total amount of the release agent contained in the parent particles is kept unchanged. As a result, while the releasability at the time of fixing remains unchanged (not deteriorated), contamination of the carrier and the charging member due to the release agent present on the surface of the toner particles containing the mother particles is suppressed, and a good result is obtained.

Generally, in low temperature fixing toner using crystalline polyester, the crystalline polyester is present in the toner in a phase separated state from the amorphous toner binder. Therefore, when the toner is melted, releasability corresponding to both phases is required. As in the present invention, toners containing two or more kinds of alkyl monoester compounds are fused or molten crystalline polyesters and amorphous toner binders (e.g., unmodified polyesters and denatureds) that are in phase separation in the toner. Considerable) to ensure the releasability of the polyester).

The incorporation of the crystalline polyester makes the formed toner have a wider fixing temperature range by making the low temperature fixability considerably superior, and the releasability is significantly excellent even at a high fixing temperature.

Crystalline polyesters are prepared between the alcohol component and the acid component and are polyesters having at least a melting point.

The crystalline polyester is a C2-C12 saturated aliphatic diol compound (particularly 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol or 1,12) as an alcohol component. Dodecanediol) or derivatives thereof, and C2-C12 dicarboxylic acids having a double bond (C = C bond) as an acid component, C2-C12 saturated dicarboxylic acids (especially fumaric acid, 1,4-butane2) Acid, 1,6-hexane2 acid, 1,8-octane2 acid, 1,10-decane2 acid or 1,12-dodecane2 acid) or derivatives thereof, preferably crystalline polyester synthesized Do.

In particular, from the standpoint of reducing the difference between the endothermic peak temperature and the endothermic shoulder temperature, the crystalline polyester may be selected from one alcohol component: 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol or 1,12-dodecanediol and one dicarboxylic acid component, ie fumaric acid, 1,4-butane diacid, 1,6-hexanoic acid, 1,8-octane diacid, 1 Preference is given to consisting of 10-decane diacid or 1,12-dodecane diacid.

Moreover, it is preferable that crystalline polyester is crystalline polyester which has a repeating structural unit represented by following General formula (1).

In formula (1), R ₁ and R ₂ each represent a hydrogen atom or a C1-C20 hydrocarbon group; n is a natural number.

An example of a method of controlling the crystallinity and softening point of the crystalline polyester is a method of suitably designing molecules such as non-linear polyester. Non-linear polyesters include an alcohol component further containing a trivalent or higher polyhydric alcohol (eg, glycerin), and an acid further containing a trivalent or higher polyhydric carboxylic acid (eg, trimellitic anhydride). It can synthesize | combine via condensation polymerization between components.

The molecular structure of the crystalline polyester can be confirmed, for example, via solid NMR.

As a result of extensive studies considering that crystalline polyesters having a sharp molecular weight distribution and low molecular weight have excellent low-temperature fixability, it is preferable to adjust the molecular weight of the crystalline polyesters as follows. Specifically, in the molecular weight distribution obtained through GPC of the soluble substance of the sample in o-dichlorobenzene, where the horizontal axis represents log (M) and the vertical axis represents mass%, preferably the peak is from 3.5 to 4.0 It is in the range of and the half width of the peak is 1.5 or less. In addition, a weight average molecular weight (Mw) is 1,000-6,500, a number average molecular weight (Mn) is 500-2,000, and Mw / Mn is 2-5.

The acid value of the crystalline polyester is not particularly limited and may be appropriately selected depending on the predetermined purpose. It is preferable that the acid value is 8 mgKOH / g-45 mgKOH / g. It is preferable that the acid value is 8 mgKOH / g or more, more preferably 20 mgKOH / g or more, and, in order to improve the high temperature offset resistance, in order to obtain a predetermined low temperature fixability from the viewpoint of the compatibility between the paper and the resin. It is because it is preferable that it is 45 mgKOH / g or less.

In addition, the hydroxyl value of the crystalline polyester is preferably 0 mgKOH / g to 50 mgKOH / g, more preferably 5 mgKOH / g to 50 mgKOH / g in order to obtain a predetermined low temperature fixability and excellent chargeability. Do.

Regarding the dispersed particle diameter of the crystalline polyester in the mother particles, it is preferable that the ratio (long axis diameter / short axis diameter) of the major axis diameter to the minor axis diameter is 3 or more, and the major axis diameter is 0.2 µm to 3.0 µm. When the ratio is less than 3 and the long axis diameter is less than 0.2 µm, it is difficult to obtain low temperature fixability in the present invention because crystalline polyester hardly exhibits crystallinity. If the major axis diameter is too large, i.e., larger than 3.0 mu m, the toner particles are greatly deformed and easily crushed in the machine. In addition, crystalline polyester having such a long axis diameter is easily exposed to the toner surface. In extreme cases, crystalline polyesters are present on the exterior of the toner, eventually contaminating the parts of the machine. That is, adjusting the long axis diameter among the dispersed particle diameters to fall within the range of 0.2 µm to 3.0 µm ensures that the alkyl monoester compound is finely dispersed in the mother particles and prevents the release agent from ubiquitous on the surface of the mother particles. .

It is preferable that crystalline polyester has the endothermic peak temperature of 50 degreeC-150 degreeC just as measured by differential scanning calorimetry (DSC). When the endothermic peak temperature is less than 50 ° C, the formed toner particles aggregate during storage at a high temperature, resulting in a decrease in heat storage resistance, whereby the toner particles easily cause blocking at the temperature of the developing apparatus. On the other hand, when the endothermic peak temperature is higher than 150 ° C., the minimum fixing temperature of the formed toner becomes high and low temperature fixability cannot be obtained.

It is preferable that the crystalline polyester is uniformly dispersed in the toner. By uniformly dispersing the crystalline polyester having the fixing aid function and the rapid melting property in the toner particles containing the parent particles, the crystalline polyester diffuses rapidly in the toner upon heating, and exhibits good releasability.

Here, the cross section of the surface of the toner particles can be observed and evaluated under a transmission electron microscope (TEM) as follows.

Specifically, the prepared toner particles are steam colored using a 5 mass% aqueous solution of commercially available ruthenium tetraoxide. The colored toner particles are embedded in an epoxy resin, and then cut using a diamond knife using a microtome (Ultracut-E) to prepare a section. The thickness of the sections is adjusted to about 100 nm based on the interference color of the epoxy resin. The prepared sections are placed on a copper grid mesh and further steam colored with a 5% by mass aqueous solution of ruthenium tetraoxide available commercially. The obtained section was observed under a transmission electron microscope (JEM-2100F, manufactured by JEOL Ltd.), and an image of the cross section of the surface of the toner particles in the section was recorded. The cross sections of the twenty toner particle surfaces are observed for the toner surface (contour of the cross section of the toner particle surface) formed of the crystalline polyester and the resin fine particles to evaluate how the resin fine particles and the crystalline polyester are present.

The toner particles themselves are colored before production of the slices as described above, so that the coloring material penetrates the surface of the toner particles. The coating film formed of the resin fine particles present on the outermost surface of the toner particles to be photographed can be observed based on the sharper difference in contrast. For example, when the coating film formed of the resin fine particles is different from the organic component in the coating film, the coating film can be distinguished from the resin in the toner particles.

In addition, the fragments may be further colored as described above to observe the crystalline polyester in clear contrast. The crystalline polyester is more lightly colored than the organic component in the toner particles. This seems to be because the degree of penetration of the coloring material into the crystalline polyester is lower than that in the case of the organic components in the toner particles, for example due to the difference in density between them. The strongly colored part contains a large amount of ruthenium atoms and is black in the image observed without emitting electron beams. On the other hand, the weakly colored portion contains a small amount of ruthenium atoms and is white in the image observed by easily emitting electron beams.

The said crystalline polyester is used as a crystalline polyester dispersion (organic solvent dispersion) which contains a binder resin in the quantity of 5 mass parts-25 mass parts with respect to 100 mass parts of a dispersion liquid. It is preferable that a crystalline polyester has an average particle diameter (dispersion diameter) of 200 nm-3,000 nm.

When the dispersion diameter of the crystalline polyester is less than 200 nm, the crystalline polyester may agglomerate inside the mother particle, and in some cases, the charge imparting effect may not be sufficiently obtained. On the other hand, when the dispersion diameter of the crystalline polyester is more than 3,000 nm, the surface characteristics of the formed toner are degraded and the carrier is contaminated, and as a result, sufficient chargeability cannot be maintained for a long time and environmental stability is also lowered.

The organic solvent dispersion liquid of the said crystalline polyester contains 5 mass parts-25 mass parts of ester bond containing binder resins other than crystalline polyester, and contains crystalline polyester in quantity with respect to 100 mass parts of dispersion liquid. It is preferable to contain in an amount. It is more preferable to contain crystalline polyester in an amount of 5 parts by mass and to contain an ester bond-containing binder resin other than crystalline polyester in an amount of 15 parts by mass. When the amount of the ester bond-containing binder resin other than the crystalline polyester is less than 5 parts by mass, the dispersion diameter of the crystalline polyester does not become small in some cases. On the other hand, when the amount of the ester bond-containing binder resin other than the crystalline polyester is more than 25 parts by mass, the organic solvent dispersion of the crystalline polyester is accompanied by aggregation of the crystalline polyester when added to the solution or dispersion of the toner material. Thus, in some cases, the low temperature fixation effect cannot be sufficiently obtained.

The crystalline polyester is heated in an organic solvent and then cooled; The resulting solution is emulsified in aqueous surfactant solution to obtain a fine dispersion; In the case where the dispersion is immediately dried for use in toner production, there may be the following problems.

(1) Since the crystalline polyester is dissolved and emulsified in an organic solvent, the particles are spherical and do not maintain a crystalline state.

(2) Even if the crystalline polyester is precipitated at the time of cooling, the coarse precipitate is emulsified and fine particles are not obtained.

(3) By drying the dispersion in the presence of a large amount of surfactant (for example, an amount corresponding to 1/5 (20 mass%) relative to the crystalline polyester), the fine particles aggregate and are coated with the surfactant. The obtained particles are directly used for toner production, and thus have insufficient dispersibility in toner. In addition, the crystalline polyester does not exhibit its effect even when melted at the time of fixing.

It is preferable that the quantity of crystalline polyester is 1 mass part-30 mass parts in addition to 100 mass parts of a parent particle. If the amount is less than 1 part by mass, in some cases, the low temperature fixing effect cannot be sufficiently obtained. On the other hand, if the amount is more than 30 parts by mass, the amount of crystalline polyester present on the outermost surface of the toner is too large, the crystalline polyester contaminates the image carrier or other members, and potentially the image quality, developer Reduces the fluidity and the image density. In addition, the surface characteristics of the formed toner are deteriorated and the carriers are contaminated, and as a result, sufficient chargeability cannot be maintained for a long time and environmental stability is also deteriorated.

Modified Polyester

The modified polyester contains at least an ester bond and bonding units other than this ester bond in its molecular structure. Such modified polyesters can be prepared from resin precursors that can produce modified polyesters. For example, the modified polyester can be produced through a reaction between a polyester containing a functional group reacting with an active hydrogen group and a compound containing an active hydrogen group.

Examples of polyesters containing functional groups that react with active hydrogen groups are, for example, polyester prepolymers containing isocyanate groups and / or epoxy groups. Such polyesters containing functional groups that react with active hydrogen groups are readily available through the reaction of polyesters (basic reactants) with conventionally known isocyanate agents (isocyanate group-containing compounds) and / or epoxidants (epoxy group-containing compounds). Can be synthesized.

For example, incorporation of a modified polyester prepared through an elongation reaction between an isocyanate group-containing polyester (polyester prepolymer) and an active hydrogen group-containing compound (e.g., an amine) into the binder resin is characterized by the lowest fixing temperature. The difference between the high temperature offset generation temperature can be large, and also improve the release range.

Examples of isocyanate agents include aliphatic polyisocyanates (eg tetramethylene diisocyanate, hexamethylene diisocyanate and 2,6-diisocyanatomethylcaproate), alicyclic polyisocyanates (eg isophorone diisocyanate and cyclo) Hexylmethane diisocyanate), aromatic diisocyanates (eg tolylene diisocyanate and diphenylmethane diisocyanate), aromatic aliphatic diisocyanates (eg, α, α, α ', α'-tetramethylxylylene Diisocyanate), isocyanurate, and products which block these polyisocyanates with phenol derivatives, oximes, caprolactams and the like. These may be used alone or in combination.

Representative examples of epoxidizing agents are epichlorohydrin.

As an example, modified polyesters (i.e., ester bonds) are formed through the reaction between an active hydrogen group-containing compound (e.g., an amine) and an isocyanate group-containing polyester that acts as a polyester having a functional group that reacts with the active hydrogen group. And modified polyesters containing urea bonds) will be described below.

In the ratio of the isocyanate agent used in the production of the isocyanate group-containing polyester, the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] to the hydroxyl group [OH] of the polyester (basic reactant) is generally 5/1. It is-1/1, it is preferable that it is 4/1-1.2 / 1, and it is more preferable that it is 2.5 / 1-1.5 / 1. When the equivalent ratio [NCO] / [OH] is more than 5, low temperature fixability may be lowered. On the other hand, when [NCO] / [OH] is less than 1, the amount of urea bonds contained in the modified polyester is small, and high temperature offset resistance may be lowered.

The amount of the isocyanate agent contained in the modified polyester is generally 0.5% by mass to 40% by mass, preferably 1% by mass to 30% by mass, and more preferably 2% by mass to 20% by mass. If the amount is less than 0.5 mass%, the high temperature offset resistance may be lowered and may be disadvantageous in achieving both the desired heat resistant storage stability and the desired low temperature fixability. If the amount is more than 40 mass%, low temperature fixability may be lowered.

The number of isocyanate groups contained per molecule in the isocyanate group-containing polyester is generally 1 or more, preferably 1.5 to 3 on average, and more preferably 1.8 to 2.5 on average. When the number per molecule is less than 1 on average, since the molecular weight of the modified polyester (urea-modified polyester) obtained after the stretching reaction is low, high temperature offset resistance may be lowered.

When amines are used as active hydrogen group-containing compounds, amines are, for example, diamine compounds, trivalent or higher polyamine compounds, amino alcohol compounds, amino mercaptan compounds, amino acid compounds, and compounds obtained by blocking the amino groups of these compounds. .

Examples of diamine compounds include: aromatic diamines (eg, phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane); Alicyclic diamines (eg, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, diaminecyclohexane and isophoronediamine); And aliphatic diamines (eg, ethylenediamine, tetramethylenediamine and hexamethylenediamine).

Examples of the trivalent or higher polyamine compound are diethylenetriamine and triethylenetetramine.

Examples of amino alcohol compounds are ethanolamine and hydroxyethylaniline.

Examples of amino mercaptan compounds are aminoethyl mercaptan and aminopropyl mercaptan.

Examples of amino acid compounds are aminopropionic acid and aminocaproic acid.

Examples of compounds obtained by blocking the amino groups of the compounds include oxazoline compounds and ketimine compounds derived from the amines and ketones (eg, acetone, methyl ethyl ketone and methyl isobutyl ketone).

Of these amines, preference is given to mixtures each consisting of a diamine and any diamine and a small amount of any polyamine. Amines can also be used as crosslinkers or extenders.

If necessary, an elongate stopper may be used to adjust the molecular weight of the modified polyester (urea-modified polyester). Examples of elongation arrestants are monoamines (eg diethylamine, dibutylamine, butylamine and laurylamine) and compounds obtained by blocking monoamines (ketimine compounds).

In the ratio of amines, the equivalent ratio [NCO] / [NHx] of the isocyanate group [NCO] in the isocyanate group-containing polyester to the amino group [NHx] in the amine is generally 1/2 to 2/1, and 1.5 / 1 to 1 / 1.5 is preferred, and 1.2 / 1 to 1 / 1.2 are more preferred. When the equivalent ratio [NCO] / [NHx] is more than 2 or less than 1/2, since the molecular weight of the urea-modified polyester obtained after the stretching reaction is low, high temperature offset resistance may be lowered.

The modified polyester (urea-modified polyester) may contain not only urethane bonds but also urea bonds. The molar ratio of the amount of urea bonds to the amount of urethane bonds (urea bonds / urethane bonds) is generally 100/0 to 10/90, preferably 80/20 to 20/80, preferably 60/40 to 30 / It is more preferable that it is 70. If the molar ratio is less than 10/90, the high temperature offset resistance may be lowered.

The modified polyester (urea-modified polyester) obtained by the stretching reaction between the isocyanate group-containing polyester and the amine is produced, for example, by a one-shot method or a prepolymer method. The weight average molecular weight of the urea-modified polyester is generally 10,000 or more, preferably 20,000 to 10,000,000, and more preferably 30,000 to 1,000,000. If this is less than 10,000, high temperature offset resistance may be degraded. The number average molecular weight of the urea-modified polyester is not particularly limited when the unmodified polyester mentioned below is further used, which may be a number average molecular weight which helps to obtain the above-mentioned weight average molecular weight. When urea-modified polyester is used alone as the binder resin, its number average molecular weight is generally 20,000 or less, preferably 1,000 to 10,000, and more preferably 2,000 to 8,000. If this is more than 20,000, low temperature fixability may be lowered, and gloss may be lowered when this urea-modified polyester is used in a full color image forming apparatus.

In the toner, the ester bond-containing binder resin (toner binder) is, for example, a binder resin containing modified polyester (i) and unmodified polyester (ii), unmodified polyester (ii) and crystalline poly Binder resin containing ester (iii), or binder resin containing modified polyester (i), unmodified polyester (ii), and crystalline polyester (iii).

For example, when using in combination with (i), (ii) and (iii), the mass ratio [(i) / (ii) + (iii)] in the toner is increased so that the toner exhibits low temperature fixability. Generally it is 5 / 95-25 / 75, it is preferable that it is 10 / 90-25 / 75, It is more preferable that it is 12 / 88-25 / 75, It is especially preferable that it is 12 / 88-22 / 78. The mass ratio [(ii) / (iii)] is generally 99/1 to 50/50, preferably 95/5 to 60/40, and more preferably 90/10 to 65/35. If the mass ratio between (i), (ii) and (iii) is outside the above preferred range, the high temperature offset resistance may be lowered and may be disadvantageous in achieving both the predetermined heat resistance and the predetermined low temperature fixability.

In the present invention, the glass transition temperature (Tg) of the ester bond-containing binder resin (toner binder) is generally 40 ° C to 70 ° C, and preferably 40 ° C to 65 ° C. If it is less than 40 ° C, the heat resistance storage of the toner may be lowered. On the other hand, if it is above 70 ° C., low temperature fixability may be insufficient.

Thanks to the presence of urea-modified polyesters as unmodified polyesters, the toner of the present invention containing the parent particles tends to be more excellent in heat resistance than known polyester toners even when the glass transition temperature is low.

The storage modulus of the ester bond-containing binder resin is not particularly limited and may be appropriately selected depending on the predetermined purpose. At a measurement frequency of 20 Hz, the temperature TG ′ having a storage modulus of 10,000 dyne / cm ² is generally 100 ° C. or higher and preferably 110 ° C. to 200 ° C. If this temperature is less than 100 ° C, the high temperature offset resistance may be lowered.

The viscosity of the toner binder is not particularly limited and may be appropriately selected depending on the desired purpose. At a measurement frequency of 20 Hz, the temperature (Tη) having a viscosity of 1,000 P is generally 180 ° C or lower, preferably 90 ° C to 160 ° C. If this temperature is above 180 ° C., low temperature fixability may be reduced. Therefore, it is preferable that TG 'is higher than Tη in view of the balance between low temperature fixability and high temperature offset resistance. In other words, the difference (TG '-Tη) between TG' and Tη is preferably 0 ° C or more, more preferably 10 ° C or more, and particularly preferably 20 ° C or more.

The upper limit of the difference between TG 'and Tη is not particularly limited.

In addition, from the viewpoint of the balance between heat storage resistance and low temperature fixability, the difference (Tη-Tg) between Tη and Tg is preferably 0 ° C to 100 ° C, more preferably 10 ° C to 90 ° C, and 20 ° C to 80 ° C. It is especially preferable that it is ° C.

The polyester contained in the ester bond-containing binder resin has a molecular weight peak of 1,000 to 30,000 and a component having a molecular weight of 30,000 or more in an amount of 1% by mass to 80% by mass, and the molecular weight distribution of the THF (tetrahydrofuran) soluble substance thereof. It is preferable that the number average molecular weight is 2,000 to 15,000. In addition, the polyester preferably contains a component having a molecular weight of 1,000 or less in an amount of 0.1% by mass to 5.0% by mass in the molecular weight distribution of the THF soluble substance of the polyester contained in the toner binder. In addition, the polyester contained in the toner binder preferably contains THF insoluble matter in an amount of 1% by mass to 15% by mass.

<Other ingredients>

Examples of other components include colorants, charge control agents and external additives.

-coloring agent-

The colorant can be any known dye or pigment. Examples of colorants include carbon black, nigrosine dye, iron black, naphthol yellow S, kanji yellow (10G, 5G and G), cadmium yellow, yellow iron oxide, yellow ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, kanji Yellow (GR, A, RN and R), Pigment Yellow L, Benzidine Yellow (G and GR), Invariant Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazin Lake, Quinoline Yellow Lake, Anthrasan Yellow BGL, Isoindolinone Yellow, Pellets, Podium, Lead Vermilion, Cadmium Red, Cadmium Mercury Red, Antimony, Invariant 4R, Parared, Picer Red, Parachloroortonitroaniline Red, Ritol Fast Scarlet G, Brilliant Fast Scarlet , Brilliant Carmine BS, Constant Red (F2R, F4R, FRL, FRLL and F4RH), Fast Scarlet VD, Vulcan Fast Rubin B, Brilliant Scarlet G, Ritol Rubin GX, Constant Red F5R, Brilliant Carmine 6B, Pigment Carlet 3B, Bordeaux 5B, Toluidin Maroon, Constant Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, BON Maroon Light, BON Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Tioindigo Red B, Tio Indigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chromium Vermilion, Benzidine Orange, Perlinon, Oil Orange, Cobalt Blue, Cyrulean Blue, Alkali Blue Lake, Peacock Blue Lake, Victoria Blue Lake , Metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS and BC), indigo, ultramarine blue, royal blue, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese violet, dioxane violet, Anthraquinone violet, chrome green, zinc rust, chromium oxide, viridian, emerald green, pigment green B, Naphthol green B, green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc flower and lithopone.

These colorants may be used alone or in combination.

The amount of the colorant is not particularly limited and may be appropriately selected depending on the predetermined purpose. The amount of the colorant is generally 1% by mass to 15% by mass with respect to toner, and preferably 3% by mass to 10% by mass.

The colorant may be mixed with the resin to form a masterbatch.

Examples of the resin used in the preparation of the masterbatch or kneaded with the masterbatch include the above-mentioned modified or unmodified polyester resins; Styrene polymers and their substitutions (eg polystyrene, poly-p-chlorostyrene and polyvinyltoluene); Styrene copolymers (eg styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-methyl acrylate copolymers, styrene-ethyl acrylate aerials) Copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-methyl α- Chloro methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indine copolymer, styrene-maleic acid air Copolymers and styrene-maleic ester copolymers); Polymethyl methacrylate; Polybutyl methacrylate; Polyvinyl chloride; Polyvinyl acetate; Polyethylene; Polypropylene, polyester; Epoxy resin; Epoxy polyol resins; Polyurethane; Polyamide; Polyvinyl butyral; Polyacrylic acid resins; rosin; Denatured rosin; Terpene resins; Aliphatic or alicyclic hydrocarbon resins; Aromatic petroleum resins; Chlorinated paraffins; And paraffin wax.

These may be used alone or in combination.

The masterbatch can be produced by mixing / kneading the masterbatch resin and the colorant by applying a high shear force. In addition, organic solvents can be used to enhance mixing between these materials. In addition, it is preferable to use a flashing method in which the aqueous paste containing the colorant is mixed / kneaded with the resin and the organic solvent, and then the colorant is transferred to the resin to remove the water and the organic solvent. This is because the cake can be used immediately (ie no need to dry). In this mixing / kneading, a high shear disperser (for example, 3 roll mill) is preferably used.

- charge control agent -

The charge control agent is not particularly limited and may be appropriately selected depending on the desired purpose. Examples include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus, Phosphorus compounds, tungsten, tungsten compounds, fluorine activators, metal salts of salicylic acid, and metal salts of salicylic acid derivatives.

The charge control agent may be a commercial item. Examples of commercially available products include nigrosine dye BONTRON 03, quaternary ammonium salt BONTRON P-51, metal-containing azo dye BONTRON S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84 and phenol condensate E -89 (all manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD), quaternary ammonium salt molybdenum complexes TP-302 and TP-415 (all from Hodogaya Chemical Co., Ltd.) and LRA-901 and boron complex LR-147 (all Japan Carlit Co., Ltd.).

The amount of the charge control agent is not particularly limited and may be appropriately selected depending on the desired purpose. It is preferable that it is 0.1 mass part-10 mass parts with respect to 100 mass parts of binder resin, and, as for the quantity of a charge control agent, it is more preferable that they are 0.2 mass part-5 mass parts. When the amount of the charge control agent is more than 10 parts by mass, the chargeability of the formed toner is too high, resulting in a reduced effect of the charge control agent. As a result, in some cases, the electrostatic force between the developing roller and the developer is increased, the fluidity of the developer is lowered, and an image with reduced color density is formed.

The charge control agent may be melt-kneaded with the masterbatch or resin prior to dissolution or dispersion. Alternatively, this may be added immediately when the toner component is dissolved or dispersed in an organic solvent in the production step of the toner material liquid (oil phase). Moreover, after formation of a mother particle, it can be fixed to the surface of a mother particle.

- Resin fine particles -

In the present invention, the resin fine particles can be used to form the parent particles. Use of resin fine particles can improve dispersion stability. In addition, the toner particles formed from the parent particles may have a narrow particle size distribution.

The resin used for the resin fine particles is an aqueous medium in which a toner material liquid (oil phase) obtained by dissolving or dispersing a toner material containing at least an ester bond-containing binder resin and / or an ester bond-containing binder resin precursor and a release agent in an organic solvent is used. When emulsified or dispersed in (aqueous phase), any resin can be used as long as it can form a predetermined emulsion or dispersion.

The resin fine particles may be a thermoplastic resin or a thermosetting resin. Examples are vinyl resins, polyurethanes, epoxy resins, polyesters, polyamides, polyimides, silicon-containing resins, phenolic resins, melamine resins, urea resins, aniline resins, ionomer resins and polycarbonates.

These may be used alone or in combination.

Among them, vinyl resins, polyurethanes, epoxy resins, polyesters and mixtures thereof are preferable from the viewpoint of easily obtaining an aqueous dispersion of spherical resin fine particles.

Vinyl resins are polymers prepared through homopolymerization or copolymerization of vinyl monomers. Examples of vinyl resins include styrene- (meth) acylate resins, styrene-butadiene copolymers, (meth) acrylic acid-acrylate polymers, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers and styrene- (meth) Acrylic acid copolymers.

The volume average particle diameter of the resin fine particles is not particularly limited and may be appropriately selected depending on the predetermined purpose. It is preferable that it is 5 nm-500 nm.

- External additives -

The toner of the present invention is formed of, for example, matrix particles of particles (colored particles) which are granulated through an emulsion of a toner material liquid (oil phase) or a desolvation of a dispersion liquid in an aqueous medium (aqueous phase). Here, in order to improve the fluidity, developability, chargeability and cleanability of the toner containing the parent particles, an external additive may be added and adhered to the surface of the mother particles.

Examples of external additives include inorganic fine particles and detergency enhancing agents.

Inorganic particulates

It is preferable that the external additive which improves fluidity | liquidity, developability, and chargeability is an inorganic fine particle. It is preferable that the primary particle diameter of an inorganic fine particle is 5 nm-2 micrometers, and it is more preferable that it is 5 nm-500 nm.

Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengal, and antimony trioxide. , Magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide and silicon nitride.

The amount of the inorganic fine particles is not particularly limited and may be appropriately selected depending on the predetermined purpose. The amount of the inorganic fine particles is preferably 0.01% by mass to 5% by mass with respect to toner, and more preferably 0.01% by mass to 2.0% by mass.

By surface-treating the inorganic fine particles to increase the hydrophobicity, the inorganic fine particles thus treated can be prevented from deteriorating the fluidity and the chargeability of the toner even under high humidity conditions. Examples of preferred surface treatment agents include silane coupling agents, silylating agents, fluorinated alkyl group-containing silane coupling agents, organic titanate-containing coupling agents, aluminum-containing coupling agents, silicone oils and modified silicone oils.

--Cleaning improver--

The detergency enhancer is used for the image carrier and the primary transfer medium in order to promote the removal of the developer (toner) remaining after the transfer. Examples include fatty acid metal salts such as zinc stearate and calcium stearate; And polymer microparticles produced via soap-free emulsion polymerization, such as polymethyl methacrylate microparticles and polystyrene microparticles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle diameter of 0.01 μm to 1 μm.

The toner is prepared by dissolving or dispersing a release agent and an ester bond-containing binder resin and / or an ester bond-containing binder resin precursor in an organic solvent to prepare a toner material liquid (oil phase); Emulsifying or dispersing this toner material liquid in an aqueous medium (aqueous phase); And it may be formed of the parent particles produced through a process comprising the step of performing a desolvation for granulation. The parent particles are prepared by drying the granulated particles obtained after desolvation or simultaneously performing desolvation and drying. Parent particles, if necessary, are sorted before being used for toner particles.

Toner particles having different specific shapes; For example, amorphous toner particles with an average circularity of less than 0.95, far from the spherical shape, do not exhibit sufficient transferability or form high quality images without dust in some cases.

In addition, a suitable measuring method of circularity is a method using an optical detection zone where a suspension containing particles passes through an image detection zone on a flat plate, and an image of the particles is optically detected by a CCD camera and then analyzed.

Here, the average circularity is a value calculated by dividing the circumferential length of a circle having the same area as the projected area obtained in this manner by the circumferential length of actual particles. The average circularity of the toner particles is preferably 0.95 to 0.99 in order to form a high resolution image having reproducibility at an appropriate concentration. It is more preferable that the average circularity of the toner particles is 0.96 to 0.99, and the amount of particles having a circularity of less than 0.96 is 10 mass% or less.

If the average circularity is 0.991 or more, cleaning defects occur on the image carrier and the transfer belt in an image forming system using a blade cleaning technique, and potentially cause stains on the image. This cleaning failure is not a problem for the development and transfer of an image having a low image occupancy because the amount of toner remaining after transfer is small. On the other hand, in the case of forming an image having a high image occupancy, for example, a photographic image, untransferred toner due to misfeeding or the like accumulates on the image carrier as residual toner after transfer, potentially causing background staining on the image, The charge rollers and the like that contact-charge the retardation are contaminated so that these charge rollers and the like do not exhibit their original chargeability.

The average circularity can be measured, for example, by a fluid particle image analyzer FPIA-2000 (manufactured by Sysmex Corp.).

One specific method of measuring average circularity is as follows: 0.1 mL to 0.5 mL of a surfactant (preferably alkylbenzene sulfonic acid salt) serving as a dispersant, containing 100 mL to 150 mL of water from which solid impurities have been removed in advance. Add to the vessel; About 0.1 g to about 0.5 g of a measurement sample (toner particles) is added to the container; Dispersing the resulting suspension containing the dispersed sample with an ultrasonic disperser for about 1 minute to about 3 minutes to adjust the concentration of the dispersion to 3,000 particles / μL to 10,000 particles / μL; The toner particles thus treated are measured in shape and distribution with the analyzer.

The volume average particle diameter (Dv) of the parent particle is not particularly limited and may be appropriately selected according to a predetermined purpose. It is preferable that it is 3.0 micrometers or more and less than 6.0 micrometers.

The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is preferably 1.05 to 1.25, more preferably 1.05 to 1.20.

Volume average particle diameter (Dv) and number average particle diameter (Dn) can be measured by MULTISIZER III (manufactured by Beckman Coulter, Inc.).

The use of the toner particles containing the parent particles prevents contamination of the charged members (e.g., carriers and charged blades), decreases in chargeability over time and toner scattering. In addition, the toner particles are excellent in all of heat resistance, low temperature fixability, and high temperature offset resistance. In particular, when used in a full color copier, the toner particles form a gloss image. Further, in the two-component developer, the toner particles have a small change in particle size in the developer even after the toner particles have been repeatedly consumed and supplied for a long time. As a result, the two-component developer containing the toner particles exhibits good and stable developability even when stirred in the developing apparatus for a long time.

Further, the one-component developer containing the toner particles has a small change in particle size even after the toner particles are repeatedly consumed and supplied. The one-component developer does not cause film formation of the toner on the developing roller, or fusion of the toner on the member (for example, the blade) for thinning the toner layer. The one-component developer can obtain good and stable developability and image formation even when used (stirred) for a long time.

In general, toner particles having a small particle diameter are more advantageous for high resolution and high quality image formation. Such toner particles are disadvantageous in transferability and detergency. When the volume average particle diameter is small (e.g., the volume average particle diameter of the parent particle is less than 3.0 mu m), the two-component developer containing the carrier and the toner having a small volume average particle diameter causes fusion of the toner on the carrier, and development As a result of prolonged stirring in the apparatus, the charge capacity of the carrier is lowered. The one-component developer containing the toner having a small volume average particle diameter easily causes film formation of the toner on the developing roller and fusing of the toner on the member (for example, the blade) for thinning the toner layer. These phenomena also occur in toners containing a large amount of fine powder (particles with even smaller particle diameters).

When the particle size of the toner is large (e.g., the volume average particle diameter of the parent particles exceeds 6.0 mu m), it is difficult to obtain a high resolution and high quality image. If the toner contained in the developer is repeatedly consumed and supplied, in many cases the change in the particle size of the toner particles becomes large. The same phenomenon occurs when the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the parent particles is greater than 1.25. When the ratio Dv / Dn is less than 1.05, in some cases, the toner is not sufficiently charged and cleaned, although there is a desirable aspect that the behavior is stabilized and uniformly charged.

(Manufacturing Method of Toner)

The method of the present invention for producing toner is a method for producing the toner of the present invention. The method of the present invention includes preparing a toner material liquid (toner material liquid preparing step), preparing an emulsion or dispersion (emulsion or dispersion preparing step), and removing a solvent (solvent removing step); If necessary, further include other steps.

<Toner Material Liquid Manufacturing Step>

In the toner material liquid manufacturing step, the toner material liquid manufacturing step comprises the steps of dissolving or dispersing at least one of an ester bond-containing binder resin and an ester bond-containing binder resin precursor and a release agent in an organic solvent to prepare a toner material liquid (oil phase). The present invention is not particularly limited and may be appropriately selected depending on the intended purpose.

The ester bond containing binder resin is the ester bond containing binder resin described above in connection with the toner of the present invention.

The ester bond-containing binder resin precursor is a resin precursor capable of producing the modified polyester described above in connection with the toner of the present invention. An example is a polyester having a functional group that reacts with an active hydrogen group.

An example of a polyester having a functional group that reacts with an active hydrogen group is an isocyanate group-containing polyester.

The toner material liquid may contain, for example, a colorant, a masterbatch, and a charge control agent.

Isocyanate group containing polyester can be synthesize | combined by the following method, for example.

First, hydroxyl group containing polyester is synthesize | combined. A hydroxyl group containing polyester can be synthesize | combined as follows, for example. Specifically, when the polyol (1) and polycarboxylic acid (2) are heated to 150 ° C to 280 ° C in the presence of a known esterification catalyst (e.g., tetrabutoxytitanate or dibutyltinoxide), Remove the water by reducing the pressure.

Then, the hydroxyl group-containing polyester can be reacted with the polyisocyanate (3) at 40 ° C to 140 ° C to obtain an isocyanate group-containing polyester.

Examples of polyol (1) include: alkylene glycols (eg, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol); Alkylene ether glycols (e.g., diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol); Alicyclic diols (eg, 1,4-cyclohexane dimethanol and hydrogenated bisphenol A); Bisphenols (e.g., bisphenol A, bisphenol F, and bisphenol S); Adducts of the alicyclic diols listed above with alkylene oxides (eg, ethylene oxide, propylene oxide and butylene oxide); And adducts of alkylene oxides (eg, ethylene oxide, propylene oxide and butylene oxide) of the bisphenols listed above.

These may be used alone or in combination.

Among these, adduct with C2-C12 alkylene glycol and bisphenol alkylene oxide (for example, 2 mole adduct of bisphenol A ethylene oxide, 2 mole adduct of bisphenol A propylene oxide, and bisphenol A propylene jade Seed 3 mole adduct) is preferred.

Trivalent or higher polyols can be used as the polyol. Examples of trivalent or higher polyols include polyhydric aliphatic alcohols (eg, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and sorbitol); Trivalent or higher phenols (eg, phenol novolac and cresol novolak); And adducts of trivalent or higher polyphenols with alkylene oxides.

These may be used alone or in combination.

Examples of the polycarboxylic acid (2) include alkylene dicarboxylic acids (eg succinic acid, adipic acid and sebacic acid); Alkenylene dicarboxylic acids (e.g., maleic acid and fumaric acid); And aromatic dicarboxylic acids (eg, terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid).

Among these, C4-C20 alkenylene dicarboxylic acid and C8-C20 aromatic dicarboxylic acid are preferable.

Trivalent or higher polycarboxylic acids can be used as the polycarboxylic acid. Examples of trivalent or higher polycarboxylic acids are C9-C20 aromatic polycarboxylic acids (eg trimellitic acid and pyromellitic acid).

It is also possible to use polycarboxylic anhydrides or lower alkyl esters (eg methyl esters, ethyl esters and isopropyl esters) instead of polycarboxylic acids.

These may be used alone or in combination.

Examples of the polyisocyanate (3) are the isocyanate agents described in connection with the toner of the present invention.

In addition, when using unmodified polyester together, this unmodified polyester can be manufactured by the same method used for manufacture of hydroxyl-containing polyester.

<Emulsion or dispersion preparation step>

The emulsion or dispersion preparation step is not particularly limited as long as the emulsion or dispersion preparation step is a step of preparing an emulsion or dispersion by emulsifying or dispersing a toner material liquid (oil phase) in an aqueous medium (aqueous phase) and suitable for a predetermined purpose. Can be chosen.

The aqueous medium is not particularly limited and may be appropriately selected depending on the desired purpose. The aqueous medium can be water alone or a mixture of water and a water miscible solvent.

Examples of water miscible solvents include alcohols (eg methanol, isopropanol and ethylene glycol), dimethylformamide, tetrahydrofuran, cellosolves (eg methyl cellosolve) and lower ketones (eg acetone and methyl) Ethyl ketone).

The aqueous medium (aqueous phase) may contain a dispersant, such as a surfactant and a polymeric protective colloid, to be described later.

When an isocyanate group-containing polyester and an amine serving as an ester bond-containing binder resin precursor are used in the production method of the toner, the isocyanate group-containing polyester and the amine are reacted together in an aqueous medium to modify the modified polyester (urea-modified poly) Esters). Alternatively, the isocyanate group containing polyester and the amine can be reacted together beforehand to form the modified polyester (urea-modified polyester).

Methods for stably forming a dispersion formed from an urea-modified polyester or an isocyanate group-containing polyester and an amine in an aqueous medium include, for example, urea-modified polyesters, other binder resins (eg, crystalline polys). Toner material liquid containing an ester) and a release agent or toner material liquid containing an isocyanate group-containing polyester, an amine, other binder resin (e.g., crystalline polyester) and a release agent to an aqueous medium, and then Is added to disperse.

Isocyanate group-containing polyesters may be mixed with other toner materials such as colorants (or colorant masterbatches), crystalline polyesters, unmodified polyesters, and charge control agents when forming dispersions in aqueous media. It is preferable to mix the toner materials together in advance, and then to disperse the resulting mixture in the aqueous medium.

In addition, in the above-described toner manufacturing method, toner materials such as colorants and charge control agents are not necessarily added to the aqueous medium prior to particle formation. These toner materials may be added after particle formation. For example, after the particle | grains which do not contain a coloring agent are formed, a coloring agent can be added to the particle | grains obtained by the well-known dyeing method.

The emulsifying or dispersing method is not particularly limited, and known dispersers such as a low speed shear disperser, a high speed shear disperser, a friction disperser, a high pressure discharge disperser or an ultrasonic disperser can be used. The method of using a high speed shear disperser is preferably used to disperse the dispersion so as to have a particle size of 2 µm to 20 µm.

In the use of the high speed shear disperser, the rotational speed is not particularly limited and may be appropriately selected depending on the desired purpose. It is generally 1,000 rpm to 30,000 rpm, preferably 5,000 rpm to 20,000 rpm.

The dispersion time is not particularly limited and may be appropriately selected depending on the predetermined purpose. This is generally from 0.1 minutes to 5 minutes when using a batch method.

The temperature at the time of dispersion is not particularly limited and may be appropriately selected depending on the predetermined purpose. It is generally 0 degreeC-150 degreeC (pressurized state), and it is preferable that they are 40 degreeC-98 degreeC. It is preferred that the temperature be high, since emulsions or dispersions formed from urea-modified polyesters (modified polyester (i)) and isocyanate group-containing polyesters can be easily dispersed due to their low viscosity.

The amount of the aqueous medium to be used is not particularly limited and may be appropriately selected depending on the predetermined purpose. This is generally 50 parts by mass to 2,000 parts by mass with respect to 100 parts by mass of the toner material liquid, and preferably 100 parts by mass to 1,000 parts by mass. When the amount of the aqueous medium used is less than 50 parts by mass, the toner material liquid cannot be sufficiently dispersed, causing a problem in the formation of toner particles having a predetermined particle size. On the other hand, it is economically disadvantageous to use aqueous media in amounts greater than 2,000 parts by mass.

If necessary, dispersants may be used. The use of a dispersant is preferable from the viewpoint of obtaining a rapid particle size distribution and realizing a stable dispersion state.

In the step of synthesizing the urea-modified polyester [modified polyester (i)] from an isocyanate group-containing polyester and an amine, the amine can be added to the aqueous medium in advance, and then the toner material containing the isocyanate group-containing polyester. The liquid may be dispersed in an aqueous medium for the reaction.

Alternatively, the toner material liquid containing the isocyanate group-containing polyester can be added to the aqueous medium, and then the amine can be added to the aqueous medium (this causes a reaction from the interface between the particles). In this case, the urea-modified polyester is preferentially formed on the surface of the formed parent particles. As a result, a concentration gradient can be formed in each particle.

In order to emulsify or disperse the toner material liquid containing the dispersed toner material (toner composition) in the aqueous medium, a surfactant may be used as the dispersant.

Examples of surfactants include anionic surfactants such as alkylbenzenesulfonic acid salts, α-olefin sulfonic acid salts and phosphate esters; Cationic surfactants such as amine salts (eg alkyl amine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives and imidazolines) and quaternary ammonium salts (eg alkyltrimethylammonium salts, dialkyl dimethylammonium salts, Alkyl dimethyl benzyl ammonium salts, pyridinium salts, alkyl isoquinolinium salts and benzethonium chloride); Nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives; And amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine.

In addition, the use of fluoroalkyl group-containing anionic surfactants as anionic surfactants can provide beneficial effects even in significantly small amounts.

The fluoroalkyl group-containing anionic surfactant is not particularly limited and may be appropriately selected depending on the predetermined purpose. Examples include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonylglutamate, sodium 3- [omega-fluoroalkyl (C6 to C11) oxy] -1 -Alkyl (C3 or C4) sulfonates, sodium 3- [omega-fluoroalkanoyl (C6 to C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11 to C20) carboxylic acids and Metal salts thereof, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonates and metal salts thereof, perfluorooctane sulfonic acid diethanol amide, N-propyl-N- ( 2-hydroxyethyl) perfluorooctanesulfon amide, perfluoroalkyl (C6-C10) sulfonamidepropyltrimethylammonium salt, salts of perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine and monopurple Fluoroalkyl (C6-C16) ethylphosphate.

Examples of commercially available products thereof include SURFLON S-111, S-112, and S-113 (manufactured by Asahi Glass Co., Ltd.); FRORARD FC-93, FC-95, FC-98 and FC-129 (manufactured by Sumitomo 3M Ltd.); UNIDYNE DS-101 and DS-102 from Daikin Industries, Ltd .; MEGAFACE F-110, F-120, F-113, F-191, F-812 and F-833 from DIC, Inc .; EFTOP EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201 and 204 from Tohchem Products Co., Ltd .; And FUTARGENT F-100 and F150 (NEOS COMPANY LIMITED).

Examples of cationic surfactants include primary, secondary or tertiary aliphatic amine acids containing fluoroalkyl groups, aliphatic quaternary ammonium salts [eg, perfluoroalkyl (C6 to C10) sulfonamide propyltrimethylammonium salts], benzal Konium salts, benzetonium chloride, pyridinium salts and imidazolinium salts.

Examples of commercially available products thereof include SURFLON S-121 (manufactured by Asahi Glass Co., Ltd.); FRORARD FC-135 (manufactured by Sumitomo 3M Ltd.); UNIDYNE DS-202 from Daikin Industries, Ltd .; MEGAFACE F-150 and F-824 from DIC, Inc .; EFTOP EF-132 from Tohchem Products Co., Ltd .; And FUTARGENT F-300 (manufactured by Neos COMPANY LIMITED).

In addition, poorly water-soluble inorganic dispersants may be used. Examples of poorly water-soluble inorganic dispersants that can be used are tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica and hydroxyapatite.

In addition, polymeric protective colloids can be used to stabilize the droplets. Examples of polymeric protective colloids are homopolymers and copolymers. Examples of monomers usable for homopolymers and copolymers include acids (eg, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid and anhydride). Maleic acid), hydroxyl-containing (meth) acrylic monomers (e.g., β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylic acid ester, di Ethylene glycol monomethacrylic acid ester, glycerin monoacrylic acid ester, glycerin monomethacrylic acid ester, N-methylolacrylamide and N-methylolmethacrylamide), vinyl alcohol Ethers thereof (eg vinyl methyl ether, vinyl ethyl ether and vinyl propyl ether), esters formed between vinyl alcohol and carboxyl group-containing compounds (eg vinyl acetate, vinyl propionate and vinyl butyrate), acrylamide, methacrylamide , Diacetone acrylamide and methylol compounds thereof; Acid chlorides (eg acrylic acid chloride and methacrylic acid chloride) and nitrogen-containing compounds and nitrogen-containing heterocyclic compounds (eg vinyl pyridine, vinyl pyrrolidone, vinyl imidazole and ethyleneimine).

Examples of polymeric protective colloids include polyoxyethylene (eg, polyoxyethylene, polyoxypropylene, polyoxyethylene alkyl amines, polyoxypropylene alkyl amines, polyoxyethylene alkyl amides, polyoxypropylene alkyl amides, polyoxyethylene Nonylphenyl ether, polyoxyethylene laurylphenyl ether, polyoxyethylene stearylphenyl ester and polyoxyethylene nonylphenyl ester); And celluloses (eg, methyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose).

When an acid or alkali soluble compound (e.g. calcium phosphate) is used as the dispersion stabilizer, the calcium phosphate used is dissolved in acid (e.g. hydrochloric acid) and then washed with water to remove from the formed fine particles. Calcium phosphate can also be removed through enzymatic digestion.

Alternatively, the dispersant used may remain on the surface of the toner particles. However, in view of the chargeability of the formed toner, it is preferable to remove the dispersant by washing.

In order to reduce the viscosity of the toner material liquid (oil phase) containing the dissolved or dispersed toner material (toner composition), a solvent capable of dissolving the modified polyester (i) and the isocyanate group-containing polyester may be further used. . The use of such a solvent is preferable at the point that a rapid particle size distribution can be obtained. It is preferable that the solvent to be used is a volatile solvent whose boiling point is less than 100 degreeC from a viewpoint of removing this solvent easily.

Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate , Ethyl acetate, methyl ethyl ketone and methyl isobutyl ketone.

These may be used alone or in combination.

Among them, the solvent is an aromatic solvent such as toluene or xylene; Or halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform or carbon tetrachloride.

The amount of the solvent used is not particularly limited and may be appropriately selected depending on the predetermined purpose. The amount of the solvent used is generally 0 parts by mass to 300 parts by mass, preferably 0 parts by mass to 100 parts by mass, and more preferably 25 parts by mass to 70 parts by mass with respect to 100 parts of the isocyanate group-containing polyester. When the solvent is used, the solvent is preferably removed by heating under normal pressure or reduced pressure after completion of the stretching and / or crosslinking reaction of the isocyanate group-containing polyester.

The elongation and / or crosslinking reaction time of the isocyanate group-containing polyester is appropriately selected depending on, for example, the reactivity between the isocyanate group-containing portion of the isocyanate group-containing polyester and the amine, and is generally 10 minutes to 40 hours, 2 It is preferable that it is time-24 hours.

The reaction temperature of the stretching and / or crosslinking reaction is not particularly limited and may be appropriately selected depending on the predetermined purpose. This is generally 0 ° C to 150 ° C and preferably 40 ° C to 98 ° C.

If desired, known catalysts can be used for the extension and / or crosslinking reactions. Examples of catalysts are dibutyltinlaurate and dioctyltinlaurate.

<Solvent Removal Step>

The solvent removal step is not particularly limited as long as the solvent removal step is a step of removing the organic solvent from the emulsion or dispersion to form the parent particles, and may be appropriately selected according to a predetermined purpose.

The method for removing the organic solvent from the emulsion or dispersion is not particularly limited and may be appropriately selected depending on the desired purpose. It is possible to use a method of gradually evaporating off the organic solvent contained in the droplets by gradually increasing the temperature of the entire system. Alternatively, by spraying the emulsion or dispersion into a dry atmosphere, a method of completely evaporating off the water-insoluble organic solvent contained in the droplets to form fine particles of the parent particles as well as evaporating off the aqueous dispersant can be used.

Dry atmospheres for spraying emulsions or dispersions generally use heated gases (e.g., air, nitrogen, carbon dioxide and combustion gases), in particular air streams heated to temperatures above or equal to the highest boiling point of the solvent used. . Even for a short time, treatment with, for example, a spray dryer, belt dryer or rotary kiln will result in a satisfactory quality of the product.

<Other steps>

Examples of other steps include washing and drying steps and classification steps.

Cleaning and drying steps

The washing and drying step is not particularly limited as long as this washing and drying step is a step of washing and drying the parent particles obtained through the solvent removal step, and may be appropriately selected according to a predetermined purpose.

Classification stage

The classification step is not particularly limited as long as this classification step is a step of performing classification after a washing and drying step, and may be appropriately selected according to a predetermined purpose.

Even when a dispersion having a wide particle size distribution is obtained at the time of emulsification or dispersion and then subjected to washing and drying steps while maintaining the particle size distribution, the dispersion may be subjected to a classification step so as to have a predetermined particle size distribution.

An example of a classification step is the removal of particles of unwanted size using, for example, cyclones, decanters or centrifuges. The classification may be carried out in the form of a powder after drying, but is preferably carried out in a liquid in view of efficiency. Fine particles or coarse particles of sorted unnecessary size can be reused in the formation of the parent particles. Here, the particulates or coarse particles may be wet or dry.

The dispersant used in the emulsion or dispersion preparation step is preferably removed from the resulting dispersion as much as possible. The dispersant may be removed in the classification step.

The powder obtained after drying (maternal particles) may optionally be mixed with heterogeneous particles such as microparticles of release agent, charge control microparticles, microparticles of fluidizing agent and colorant microparticles, and optionally, mechanical impact on the resulting mixture results in By being fixed or fused on the mother particles, toner particles (toner particles containing the mother particles) formed from the mother particles are obtained. Applying a mechanical impact can prevent the heterogeneous particles from falling off from the surface of the toner particles containing the obtained parent particles.

Examples of mechanical impact methods include the use of high-speed rotating blades to impact the mixture and forcing the mixture through high velocity airflow to accelerate and impinge the agglomerated or complex particles onto an appropriate collision plate. There is a way.

Examples of devices used to exert mechanical impacts include ONGMILL (manufactured by Hosokawa Micron Corp.), an I-type mill (manufactured by Nippon Neumatic Co., Ltd.) and manufactured to reduce its grinding air pressure, HYBRIDIZATION SYSTEM ( Nara Machinery Co., Ltd.), CRYPTRON system (manufactured by Kawasaki Heavy Industries, Ltd.) and auto trigger.

(Developer)

The developer of the present invention contains the above-described toner of the present invention; If necessary, it further contains other components such as a carrier (magnetic carrier).

The developer may be a one-component developer composed of toner or a two-component developer.

When the developer is used as a two-component developer, the ratio between the carrier and the toner contained in the developer is not particularly limited and may be appropriately selected depending on the predetermined purpose. The amount of toner is 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the carrier.

The carrier is not particularly limited and may be appropriately selected depending on the desired purpose. Examples are iron powder, ferrite powder, magnetite powder and magnetic resin carrier.

The carrier is preferably coated. Examples of coating materials used are urea-formaldehyde resins, melamine resins, benzoguanamine resins, urea resins, polyamide resins and epoxy resins.

Further examples of coating materials include acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins and polyvinyl butyral resins; Halogenated olefin resins such as polyvinyl chloride; Polyester-based resins such as polyethylene terephthalate resin and polybutylene terephthalate resin; Polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride and vinyl fluoride Fluoro terpolymers of copolymers, tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers; And silicone resins.

If desired, conductive powder or the like may be incorporated into the coating material. The conductive powders that can be used are preferably metal powders, carbon black, titanium oxide, tin oxide and zinc oxide. It is preferable that the average particle diameter of an electroconductive powder is 1 micrometer or less. If the average particle diameter exceeds 1 mu m, it may be difficult to control the electrical resistance.

(Developer container)

The developer accommodating container of the present invention is not particularly limited as long as it is a container accommodating the developer of the present invention and may be appropriately selected according to a predetermined purpose. An example of a container is a container having a container body and a cap.

The shape, structure, material, etc. of the container body are not particularly limited and may be appropriately selected depending on the predetermined purpose.

<Shape>

Its shape is not particularly limited and may be appropriately selected depending on the desired purpose. It is preferable that a container main body has a hollow-cylindrical shape, for example. It is particularly preferable that the hollow cylindrical body is provided with a spirally arranged inner surface and which is partially or fully folded and in which the contained developer can be transferred to the outlet port by rotation.

<Material>

The material thereof is not particularly limited and may be appropriately selected depending on the predetermined purpose. This is preferably a material with high dimensional accuracy. Examples of materials include polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl chloride resins, polyacrylic resins, polycarbonate resins, ABS resins and polyacetal resins.

<Use>

The toner container is excellent in handleability; That is, it is suitable for storing, conveying, etc., and is detachably mounted to a process cartridge, an image forming apparatus, or the like, and is suitably used to supply a developer.

The developer accommodating container can be used as the toner container for accommodating the above-mentioned toner.

(Image formation method)

An image forming method of the present invention comprises the steps of: charging a surface of an image bearing member; Exposing the surface of the charged image bearing to form an electrostatic latent image on the image bearing; Developing a latent electrostatic image formed on the image carrier with a developer containing toner to form a toner image on the image carrier; Transferring the toner image onto a recording medium; And fixing the transferred image on the recording medium; If necessary, include additional steps.

The toner is the toner of the present invention.

The image forming method can be implemented, for example, with an electrophotographic image forming apparatus schematically shown in FIG. Next, a schematic configuration of the image forming apparatus shown in FIG. 1 will be described.

While the image carrier 1 is rotated in the direction indicated by the arrow, the surface of the image carrier is uniformly charged by the charging member 2. Subsequently, the image bearing member 1 is irradiated with the image light r from the exposure means in the exposure portion located in the downstream portion of the charging member 2 in the rotational direction of the image bearing member. Through this light irradiation, electric charges are lost in the portion of the surface of the image carrier on which the image light r is irradiated. As a result, an electrostatic latent image corresponding to the image light is formed on the surface of the image carrier 1.

The developing device 3 serving as the developing means is disposed at a downstream portion of the exposed portion. The developing apparatus 3 contains the toner 4 as a developer. The toner 4 is stirred / mixed with a paddle (stirring mechanism) 14 provided with the conveying screw 13 and frictionally charged to have a predetermined polarity. Then, the toner is conveyed to the nip portion (developing area) between the developing sleeve 5 and the image bearing member 1 by the developing sleeve 5. The toner conveyed to the developing region is transferred from the surface of the developing sleeve 5 to the surface of the image bearing member 1 by the action of the developing electric field formed in the developing region by the developing bias applying means, so that the toner is transferred to the surface of the image bearing member. Is attached to. As a result, the electrostatic latent image formed on the surface of the image bearing member is developed into a toner image (visible image).

The toner image formed on the image carrier 1 in this manner is transferred onto the transfer sheet S serving as a recording medium. Prior to the image transfer, the transfer sheet is formed by the registration roller 18 between the transfer carrier belt 6 (which serves as a transfer means) and the image bearing member 1 disposed downstream of the developing apparatus 3. It is supplied to the transfer region, which is a gap portion, and comes into close contact with the image bearing member 1. Then, the toner image transferred onto the transfer sheet is fixed by a fixing roller (which serves as fixing means) disposed at a downstream portion thereof in the rotational direction of the transfer conveyance belt 6. Thereafter, the transfer sheet is discharged onto the discharge tray outside the apparatus main body by the discharge means. Note that reference numeral 6a in FIG. 1 denotes a bias roller.

The toner (residual toner) remaining on the image carrier 1, which is not transferred onto the transfer paper sheet in the transfer area, is disposed on the cleaning blade 7, disposed in a downstream portion of the transfer area in the rotational direction of the image carrier. It is removed from the image carrier 1 by a cleaning device (which serves as a cleaning unit) including a spring 8 and a recovery coil 9. Further, residual charge remaining on the image carrier 1 after cleaning the residual toner is removed by the static eliminator 20 including the antistatic lamp. In Fig. 1, reference numeral 16 denotes a reflection density detection sensor (P sensor), reference numeral 17 denotes a toner density sensor, and reference numeral 10 denotes an image carrier and a cleaning unit (PCU).

Example

The present invention will be described below by way of examples, but should not be construed as limiting the invention thereto. Unless otherwise specified, unit "part" means "mass part" and unit "%" means "mass%".

First, the materials required to form the toners of the Examples and Comparative Examples were prepared as follows.

[Synthesis example of synthetic ester wax (alkyl monoester compound)]

(Synthesis Example 1)

Stearic Acid (Express Reagent, manufactured by Kishida Chemical Co., Ltd.) (284 g, 1 mol), Stearyl Alcohol (Express Reagent, manufactured by Kishida Chemical Co., Ltd.) (256 g, 1 mol), and Sulfuric Acid (20 mL) was placed in a round bottom flask equipped with a stirrer and a condenser and then refluxed at 130 ° C. for 4 hours while removing the water formed. The product was purified by dimethyl ether to give [synthetic ester wax (1)].

(Synthesis Example 2)

Behenic acid (EP grade, product of Tokyo Chemical Industry Co., Ltd.) (340 g, 1 mol), cetyl alcohol (Express reagent, manufactured by Kishida Chemical Co., Ltd.) (242 g, 1 mol) and sulfuric acid (20 mL) was placed in a round bottom flask equipped with a stirrer and a condenser and then refluxed at 130 ° C. for 4 hours while removing the water formed. The product was purified with diisopropyl ether to give [synthetic ester wax (2)].

(Synthesis Example 3)

Behenic acid (EP grade, product of Tokyo Chemical Industry Co., Ltd.) (340 g, 1 mole), stearyl alcohol (special reagent, product of Kishida Chemical Co., Ltd.) (256 g, 1 mole) and sulfuric acid ( 20 mL) was placed in a round bottom flask equipped with a stirrer and a condenser and then refluxed at 150 ° C. for 5 hours while removing the water formed. The product was purified with diisopropyl ether to give [synthetic ester wax (3)].

(Synthesis Example 4)

Behenic acid (EP grade, manufactured by Tokyo Chemical Industry Co., Ltd.) (340 g, 1 mol), Eicosanol (EP grade, manufactured by Tokyo Chemical Industry Co., Ltd.) (284 g, 1 mol), and sulfuric acid ( 20 mL) was placed in a round bottom flask equipped with a stirrer and a condenser and then refluxed at 200 ° C. for 5 hours while removing the water formed. The product was purified with diisopropyl ether to give [synthetic ester wax (4)].

Synthesis Example 5

Stearic Acid (Express Reagent, manufactured by Kishida Chemical Co., Ltd.) (284 g, 1 mol), Cetyl Alcohol (Express Reagent, manufactured by Kishida Chemical Co., Ltd.) (242 g, 1 mol), and sulfuric acid (20 mL ) Was placed in a round bottom flask equipped with a stirrer and a condenser and then refluxed at 200 ° C. for 5 hours while removing the water formed. The product was purified with diisopropyl ether to give [synthetic ester wax (5)].

(Synthesis Example 6)

Myristic acid (EP grade reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) (228 g, 1 mol), Cetyl alcohol (Express reagent, manufactured by Kishida Chemical Co., Ltd.) (242 g, 1 mol), and sulfuric acid (20 mL) was placed in a round bottom flask equipped with a stirrer and a condenser and then refluxed at 200 ° C. for 5 hours while removing the water formed. The product was purified with diisopropyl ether to give [synthetic ester wax (6)].

(Synthesis Example 7)

Myristic acid (EP grade reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) (228 g, 1 mol), Myristyl alcohol (CONOL 1495, manufactured by New Japan Chemical Co., Ltd.) (200 g, 1 mol) And sulfuric acid (20 mL) were placed in a round bottom flask equipped with a stirrer and a condenser and then refluxed at 200 ° C. for 5 hours while removing the water formed. The product was purified with diisopropyl ether to give [synthetic ester wax (7)].

Table 1 below shows the carbon number distribution of each of the synthetic ester waxes (1) to (7) prepared above (i.e., the amount (mass%) of alkyl monoester compounds having the number of carbon atoms shown in Table 1). Table 2 below shows their physical properties.

[Table 1]

The carbon number distribution of each synthetic ester wax was measured by ¹³ C-NMR using a nuclear magnetic resonance spectrometer (JEOL Ltd.).

[Table 2]

Melting | fusing point was calculated | required based on the endothermic peak temperature which becomes the maximum endothermic amount in the differential scanning calorimetry analysis curve obtained through differential scanning calorimetry (DSC).

Melt viscosity at 100 ° C. was measured with a Brookfield Rotational Viscometer.

[Manufacture of Water Phase]

(Synthesis Example 8)

Synthesis of Emulsion of Organic Fine Particles

A reaction vessel equipped with a stirring rod and a thermometer was provided with 700 parts of water, 12 parts of sodium salt of sulphate of ethylene oxide adduct of methacrylic acid (Eleminol RS-30, manufactured by Sanyo Chemical Industries, Ltd.), 140 parts of styrene, methacrylic acid Filled with 140 parts and 1.5 parts of ammonium persulfate. The resulting mixture was stirred at 450 rpm for 20 minutes. The system of the obtained white emulsion was raised to 75 ° C. and then reacted for 5 hours. Subsequently, 35 parts of 1% aqueous ammonium persulfate solution was added to the resulting emulsion, and the resulting mixture was aged at 75 ° C. for 5 hours to produce a vinyl resin (styrene-methacrylic acid of sulfate of ethylene oxide adduct of methacrylic acid). -Copolymer of sodium salt) to obtain an aqueous dispersion [particulate dispersion 1].

Measurements with LA-920 (laser diffraction / scattering particle size analyzer, manufactured by HORIBA, Ltd.) found that the volume average particle diameter of [particulate dispersion 1] was 0.30 μm. A part of [particulate dispersion 1] was dried, and resin was isolate | separated. It was found that the Tg of this resin was 155 ° C.

&Lt; Preparation of water phase &

Water (1,000 parts), 85 parts of [particulate dispersion 1], 40 parts of a 50% aqueous solution of sodium dodecyldiphenylethersulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.) and 95 parts of ethyl acetate are mixed together to give a milky white color. Was prepared as a [water phase 1].

[Synthesis of low molecular weight polyester 1 <hydroxyl group-containing polyester>]

(Synthesis Example 9)

A reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube was charged with 235 parts bisphenol A ethylene oxide 2 mole adduct, 535 parts bisphenol A propylene oxide 3 mole adduct, 215 parts terephthalic acid, 50 parts adipic acid and 3 parts di Filled with butyltinoxide. The resulting mixture was reacted for 10 hours at 240 ° C. under normal pressure, and then for 6 hours at a reduced pressure of 10 mmHg to 20 mmHg. Thereafter, 45 parts of trimellitic anhydride were added to the reaction vessel, and then reacted at 185 ° C. for 3 hours under normal pressure to prepare [Low Molecular Weight Polyester 1].

The low molecular weight polyester 1 was found to have a number average molecular weight of 2,800, a weight average molecular weight of 7,100, a Tg of 45 ° C, and an acid value of 22 mgKOH / g.

[Synthesis of low molecular weight polyester 2 <hydroxyl group-containing polyester>]

(Synthesis Example 10)

The reaction vessel with a condenser, stirrer and nitrogen introduction tube was filled with 125 parts of propylene glycol, 632 parts of bisphenol A propylene oxide 3 mole adduct, 150 parts of terephthalic acid, 100 parts of adipic acid and 3 parts of dibutyltinoxide. The resulting mixture was reacted for 10 hours at 240 ° C. under normal pressure, and then for 6 hours at a reduced pressure of 10 mmHg to 20 mmHg. Thereafter, 65 parts of trimellitic anhydride was added to the reaction vessel, followed by reaction at 185 ° C. for 3 hours under normal pressure to prepare [low molecular weight polyester 2].

Low molecular weight polyester 2 was found to have a number average molecular weight of 3,500, a weight average molecular weight of 8,200, a Tg of 55 ° C and an acid value of 32 mgKOH / g.

[Synthesis of styrene acrylic resin 1]

(Synthesis Example 11)

A reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube was used to prepare 700 parts of styrene monomer, 300 parts of n-butyl methacrylate, 1,000 parts of toluene, 10 parts of methacrylic acid, 3 parts of azobisisobutylonitrile and 0.2 parts of dodecyl. Filled with mercaptan. The resulting mixture was reacted at 90 DEG C for 10 hours at normal pressure, and then at 120 DEG C for 6 hours. [Styrene acrylic resin 1] was obtained by treating the obtained resin solution at 50 DEG C and reduced pressure of 10 mmHg to 20 mmHg for 6 hours to remove toluene.

[Styrene Acrylic Resin 1] found that the number average molecular weight was 4,300, the weight average molecular weight was 8,600, Tg was 62 ° C, and the acid value was 15 mgKOH / g.

[Synthesis of Intermediate Polyester]

(Synthesis Example 12)

A reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube was charged with 700 parts of bisphenol A ethylene oxide 2 mole adduct, 85 parts of bisphenol A propylene oxide 2 mole adduct, 300 parts terephthalic acid, 25 parts trimellitic anhydride and 3 parts Filled with dibutyltinoxide. The resulting mixture was reacted for 10 hours at 240 ° C. under normal pressure, and then for 6 hours at a reduced pressure of 10 mmHg to 20 mmHg to obtain [Intermediate Polyester 1].

[Intermediate Polyester 1] was found to have a number average molecular weight of 2,500, a weight average molecular weight of 10,000, a Tg of 58 ° C, an acid value of 0.5 mgKOH / g, and a hydroxyl value of 52 mgKOH / g.

[Synthesis of isocyanate group-containing polyester (prepolymer)]

(Synthesis Example 13)

The reaction vessel equipped with the condenser, the stirrer and the nitrogen introduction tube was then filled with 400 parts of [Intermediate Polyester 1], 90 parts of isophorone diisocyanate and 500 parts of ethyl acetate. The resulting mixture was reacted at 110 ° C. for 6 hours to obtain [Prepolymer 1].

It was found that the amount of free isocyanate contained in [Prepolymer 1] was 1.67 mass%, and the solid content of [Prepolymer 1] was 50%.

Synthesis of Crystalline Polyester

(Synthesis Example 14)

A 5-L four-necked flask, equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, was prepared with 1,4-butanediol (28 mol), fumaric acid (24 mol), trimellitic anhydride (1.80 mol) and hydroquinone (6.0 g). It was filled with, and then reacted at 150 ° C. for 6 hours. The reaction mixture was reacted at 200 ° C. for 1 hour, and further reacted at 8.3 kPa for 1 hour to obtain [crystalline polyester 1].

[Crystalline Polyester 1] has a melting point of 125 ° C. (endothermic peak temperature in DSC), a number average molecular weight of 1,800, a weight average molecular weight of 6,000, an acid value of 26 mgKOH / g, and a hydroxyl value of 30 mgKOH / found to be g.

(Synthesis Example 15)

A 5-L four-necked flask, equipped with a nitrogen introduction tube, dehydration tube, stirrer and thermocouple, was prepared with 1,10-decanediol (13 mol), 1,8-octanediol (17 mol), fumaric acid (26 mol), anhydrous tree It was filled with melic acid (1.80 mol) and 4.9 g of hydroquinone and then reacted at 180 ° C. for 10 hours. The reaction mixture was reacted at 200 ° C. for 3 hours, and further reacted at 8.3 kPa for 2 hours to synthesize [crystalline polyester 2].

[Crystalline Polyester 2] has a melting point of 70 ° C. (endothermic peak temperature in DSC), a number average molecular weight of 3,000, a weight average molecular weight of 10,000, an acid value of 21 mgKOH / g, and a hydroxyl value of 28 mgKOH / found to be g.

Synthesis of Ketamine

(Synthesis Example 16)

A reaction vessel equipped with a stirring rod and a thermometer was filled with 180 parts of isophoronediamine and 80 parts of methyl ethyl ketone, and then reacted at 50 ° C. for 6 hours to obtain [Ketamine Compound 1].

[Ketamine Compound 1] found that the amine value was 420.

[Synthesis of Master Batch (MB)]

(Synthesis Example 17)

Water (1,300 parts), 550 parts of carbon black (Printex35, manufactured by Deggusa Co.) (DBP oil absorption = 43 mL / 100 mg, pH = 9.5) and 1,300 parts of low molecular weight polyester 1 were prepared by HENSCHEL MIXER (Mitsui Mining Co. Mixed together). Using a two-roll mill, the resulting mixture was kneaded at 160 ° C. for 45 minutes, then rolled, cooled, and ground with a grinder to obtain [MasterBatch 1].

(Example 1)

Preparation of Toner of Example 1

Preparation of Wax Dispersion 1

A vessel equipped with a stirring rod and a thermometer was prepared from 400 parts of [low molecular weight polyester 1], a synthetic ester wax (mixture) as shown in Tables 3-1 and 3-2 below [ie, a synthetic ester wax (1) Mixture of mass ratio (1) / (2) of (2) of 50/50] and 1,000 parts of ethyl acetate. The resulting mixture was then heated to 80 ° C. under stirring, held at 80 ° C. for 8 hours, and cooled to 24 ° C. for 1 hour. The obtained dispersion was fed at a feed rate of 1 kg / hour; Disk circumferential speed: 6 m / sec; Amount of injected 0.5 mm (diameter) -zirconia beads: 80% by volume; And a wax mill (manufactured by Ultra Visco Mill, manufactured by Aymex Co.) under the conditions of pass time: 3 to disperse the synthetic ester wax (WAX) to obtain [Wax Dispersion Liquid 1].

[Wax Dispersion 1] was measured for the dispersion diameter using LA-920, and [Wax Dispersion 1] was found to have an average particle diameter (wax dispersion particle diameter) of 0.15 mu m.

<Production of pigment, WAX dispersion liquid 1>

480 parts of [MasterBatch 1] were then added to the above prepared [Wax Dispersion 1]. Subsequently, [Wax Dispersion 1] was fed at a liquid feeding rate of 1 kg / hour; Disk circumferential speed: 6 m / sec; Amount of injected 0.5 mm-zirconia beads: 80% by volume; And carbon black and WAX were dispersed by treating with a beads mill (Ultra Visco Mill, manufactured by Aymex Co.) under the condition of Pass number: 3. Further, 1,000 parts of a 65% ethyl acetate solution of [Low Molecular Weight Polyester 1] was added thereto, and the resulting mixture was treated once with a bead mill under the same conditions to obtain [Pigment-WAX Dispersion Liquid 1].

The concentration of the solids content of [Pigment / WAX Dispersion 1] was adjusted by evaporation of ethyl acetate, and then concentrated so that the solids content was 53% (measured after drying at 130 ° C. for 30 minutes). Got.

<Production of Toner Matrix Particles 1>

The following emulsification, desolvation, washing and drying steps were carried out to obtain parent particles.

<< oil painting >>

[Pigment and WAX dispersion 1] (780 parts), 120 parts of [Prepolymer 1] and 5 parts of [Ketamine Compound 1] were placed in a container. The resulting mixture was mixed together for 1 minute at 6,000 rpm with a TK homomixer (PRIMIX Corporation) to prepare an oil phase. Subsequently, 1,300 parts of [water phase 1] were added to the vessel, and then mixed with TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsified slurry 1].

<< desolventization >>

[Emulsification slurry 1] was added to a vessel equipped with a stirrer and a thermometer, and then desolvated at 30 ° C for 10 hours, and aged at 45 ° C for 5 hours to obtain [Dispersion Slurry 1].

<< cleaning and drying >>

[Dispersion slurry 1] (100 parts) was filtered under reduced pressure, and then a series of treatments (1) to (4) described below were carried out twice to obtain [filtration cake 1]:

(1): Ion-exchanged water (100 parts) was added to the filter cake, and then mixed with a TK homomixer (10 minutes at 12,000 rpm), followed by filtration;

(2): 10% aqueous sodium hydroxide solution (100 parts) was added to the filter cake obtained in (1), and then mixed with a TK homomixer (30 minutes at 12,000 rpm), followed by filtration under reduced pressure;

(3): 10% hydrochloric acid (100 parts) was added to the filter cake obtained in (2), followed by mixing with a TK homomixer (10 minutes at 12,000 rpm), followed by filtration;

(4): Ion-exchanged water (300 parts) was added to the filter cake obtained in (3), and then mixed with a TK homomixer (10 minutes at 12,000 rpm), followed by filtration.

[Filter Cake 1] was dried for 48 hours at 45 DEG C with a pure air dryer, and then passed through a sieve having a mesh size of 75 mu m to prepare [Material Particle 1].

[Mother Particle 1] was found to have a volume average particle diameter (Dv) of 5.35 µm and a ratio (Dv / Dn) of volume average particle diameter (Dv) to number average particle diameter (Dn) of 1.08.

In addition, the volume average particle diameter (Dv) and the number average particle diameter (Dn) were measured by MULTISIZER III (manufactured by Beckman Coulter, Inc.).

The obtained parent particles (100 parts) were mixed with hydrophobic silica (0.7 parts) and hydrophobic titanium oxide (0.3 parts) using HENSCHEL MIXER to prepare a toner containing the parent particles (toner of Example 1). .

Table 3-1 and Table 3-2 below collectively present the combination and mixing ratio of the synthetic ester wax, the type of binder resin used, and the like.

In addition, Table 4 below summarizes the particle diameter of the wax dispersion, the volume average particle diameter of the parent particles, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the parent particles.

(Preparation of toners of Examples 2 to 4 and Comparative Examples 1 to 5)

The wax dispersions were prepared by repeating the procedure of Example 1 except that the combination and mixing ratio of the synthetic ester waxes were changed as shown in Tables 3-1 and 3-2 below while keeping the total amount of the release agent unchanged. By doing so, the mother particles of Examples 2 to 4 and Comparative Examples 1 to 5 were prepared.

In the same manner as in Example 1, the parent particles of the obtained Examples 2 to 4 and Comparative Examples 1 to 5 were mixed with the inorganic fine particles to prepare the toners of Examples 2 to 4 and Comparative Examples 1 to 5.

Table 4 below, in the same manner as in Example 1, the particle size of the wax dispersion; Volume average particle diameter of the parent particle; And the results obtained by measuring the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the parent particles.

(Example 5)

Preparation of Toner of Example 5

Preparation of Wax Dispersion 5

A vessel equipped with a stirring rod and a thermometer was prepared using 400 parts of [low molecular weight polyester 1], synthetic ester waxes (mixtures) as shown in Tables 3-1 and 3-2 below [ie, synthetic ester waxes (1) and ( Mixture having a mass ratio (1) / (4) of 4) of 50/50] and 1,000 parts of ethyl acetate. The resulting mixture was then heated to 80 ° C. under stirring, held at 80 ° C. for 8 hours, and cooled to 24 ° C. for 1 hour. The obtained dispersion was fed at a feed rate of 1 kg / hour; Disk circumferential speed: 6 m / sec; Amount of injected 0.5 mm (diameter) -zirconia beads: 80% by volume; And a number of passes: 3, and treated with a bead mill (Ultra Visco Mill, manufactured by Aymex Co.) to disperse the synthetic ester wax (WAX) to obtain [Wax Dispersion 5].

[Wax Dispersion 5] was measured for the dispersion diameter using LA-920, and [Wax Dispersion 5] was found to have an average particle diameter (wax dispersion particle diameter) of 0.22 mu m.

Preparation of Crystalline Polyester Dispersion 1

Crystalline polyester resin 1 (110 g) and ethyl acetate (450 g) were added to a 2 L metal container. The resulting mixture was dissolved and dispersed under heating at 80 ° C. and then quenched in an ice water bath. Thereafter, glass beads (3 mm in diameter) (500 mL) were added to the mixture, followed by stirring for 10 hours with a batch sand mill (manufactured by Kanpe Hapio Co., Ltd.), thereby obtaining a [crystal] having a volume average particle diameter of 0.4 [mu] m. Sexual Polyester Dispersion 1] was obtained.

<Production of pigment, WAX dispersion 5>

Then, 480 parts of [Masterbatch 1] and 1,000 parts of [crystalline polyester dispersion 1] were added to [wax dispersion 5] prepared above. Subsequently, [Wax Dispersion 5] was fed at a feed rate of 1 kg / hour; Disk circumferential speed: 6 m / sec; Amount of injected 0.5 mm (diameter) -zirconia beads: 80% by volume; And carbon black, WAX and [crystalline polyester dispersion 1] were dispersed by treatment with a bead mill (Ultra Visco Mill, manufactured by Aymex Co.) under the condition of Pass number: 3. Further, 1,000 parts of a 65% ethyl acetate solution of [Low Molecular Weight Polyester 1] was added thereto, and the resulting mixture was treated once with a bead mill under the same conditions to obtain [Pigment-WAX Dispersion 5].

The concentration of the solid content of [Pigment / WAX Dispersion 5] was adjusted by evaporation of ethyl acetate, and then concentrated so that the solid content was 53% (measured after drying at 130 ° C. for 30 minutes). Got.

<Production of Toner Matrix Particles 5>

The following emulsification, desolvation, washing and drying steps were carried out to obtain parent particles.

<< oil painting >>

[Pigment and WAX dispersion 5] (780 parts), 120 parts of [Prepolymer 1] and 5 parts of [Ketamine Compound 1] were placed in a container. The resulting mixture was mixed together for 1 minute at 6,000 rpm with a TK homomixer (PRIMIX Corporation). Subsequently, 1,300 parts of [water phase 1] were added to the vessel, and then mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsified slurry 5].

<< desolventization >>

[Emulsification slurry 5] was added to a vessel equipped with a stirrer and a thermometer, and then desolvated at 30 ° C. for 10 hours and aged at 45 ° C. for 5 hours to obtain [Dispersion Slurry 5].

<< cleaning and drying >>

[Dispersion slurry 5] (100 parts) was filtered under reduced pressure, and then a series of treatments (1) to (4) described below were carried out twice to obtain [filtration cake 5]:

(1): Ion-exchanged water (100 parts) was added to the filter cake, and then mixed with a TK homomixer (10 minutes at 12,000 rpm), followed by filtration;

(2): 10% aqueous sodium hydroxide solution (100 parts) was added to the filter cake obtained in (1), and then mixed with a TK homomixer (30 minutes at 12,000 rpm), followed by filtration under reduced pressure;

(3): 10% hydrochloric acid (100 parts) was added to the filter cake obtained in (2), and then mixed with a TK homomixer (10 minutes at 12,000 rpm), followed by filtration;

(4): Ion-exchanged water (300 parts) was added to the filter cake obtained in (3), and then mixed with a TK homomixer (10 minutes at 12,000 rpm), followed by filtration.

[Filter Cake 5] was dried for 48 hours at 45 DEG C with a pure air dryer, and then passed through a sieve having a mesh size of 75 mu m to prepare [Material Particle 5].

[Mother Particle 5] was found to have a volume average particle diameter (Dv) of 5.20 µm and a ratio (Dv / Dn) of volume average particle diameter (Dv) to number average particle diameter (Dn) of 1.10.

The obtained mother particles (100 parts) were mixed with hydrophobic silica (0.7 parts) and hydrophobic titanium oxide (0.3 parts) using HENSCHEL MIXER to prepare a toner containing the mother particles (toner of Example 5). .

It was also found that the dispersion diameter of the release agent in the parent particles was 0.12 μm. It was found that the dispersed particle diameter of the crystalline polyester in the parent particles was 0.2 μm to 3.0 μm in long axis diameter.

Table 4 below summarizes the particle diameter of the wax dispersion, the volume average particle diameter of the parent particles, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the parent particles.

(Example 6)

Preparation of Crystalline Polyester Dispersion 2

Crystalline polyester resin 2 (110 g) and ethyl acetate (450 g) were added to a 2 L metal container. The resulting mixture was dissolved and dispersed under heating at 80 ° C. and then quenched in an ice water bath. Thereafter, glass beads (3 mm in diameter) (500 mL) were added to the mixture, followed by stirring for 10 hours with a batch sand mill (manufactured by Kanpe Hapio Co., Ltd.) to obtain a crystal having a volume average particle diameter of 0.45 mu m. Sexual Polyester Dispersion 2] was obtained.

Preparation of Toner of Example 6

A wax dispersion was prepared by repeating the procedure of Example 5, except that the combination and mixing ratio of the synthetic ester wax was changed as shown in Tables 3-1 and 3-3 below while keeping the total amount of the release agent unchanged. And the procedure of Example 5 was repeated except that [Crystalline Polyester Dispersion 1] was changed to [Crystalline Polyester Dispersion 2], thereby preparing the parent particle of Example 5.

Wax dispersions were measured for dispersion diameter using LA-920, and the wax dispersions were found to have an average particle diameter (wax dispersion particle diameter) of 0.14 μm.

The obtained toner base particles were found to have a volume average particle diameter (Dv) of 5.10 mu m and a ratio (Dv / Dn) of volume average particle diameter (Dv) to number average particle diameter (Dn) of 1.12.

The obtained mother particles were mixed with the inorganic fine particles in the same manner as in Example 5 to prepare the toner of Example 6.

It was also found that the dispersion diameter of the release agent in the parent particles was 0.10 μm. It was found that the dispersed particle diameter of the crystalline polyester in the parent particles was 0.2 μm to 3.0 μm in long axis diameter.

Table 4 below summarizes the particle diameter of the wax dispersion, the volume average particle diameter of the parent particles, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the parent particles.

(Example 7)

Preparation of Toner of Example 7

Preparation of Wax Dispersion 7

A vessel equipped with a stirring rod and a thermometer was prepared from 200 parts of [low molecular weight polyester 1], synthetic ester waxes (mixtures) as shown in Tables 3-1 and 3-2 below [ie, synthetic ester waxes (1) and ( A mixture having a mass ratio (1) / (2) of 2) of 50/50] and 1,000 parts of ethyl acetate. The resulting mixture was then heated to 80 ° C. under stirring, held at 80 ° C. for 8 hours, and cooled to 24 ° C. for 1 hour. The obtained dispersion was fed at a feed rate of 1 kg / hour; Disk circumferential speed: 6 m / sec; Amount of injected 0.5 mm (diameter) -zirconia beads: 80% by volume; And a number of passes: 3, and treated with a beads mill (Ultra Visco Mill, manufactured by Aymex Co.) to disperse the synthetic ester wax (WAX) to obtain [Wax Dispersion 7].

[Wax Dispersion 7] was measured for the dispersion diameter using LA-920, and [Wax Dispersion 7] was found to have an average particle diameter (wax dispersion particle diameter) of 0.19 mu m.

<Production of pigment, WAX dispersion liquid 7>

480 parts of [MasterBatch 1] were then added to the above prepared [Wax Dispersion 7]. Subsequently, [Wax Dispersion Liquid 7] was fed at a feed rate of 1 kg / hour; Disk circumferential speed: 6 m / sec; Amount of injected 0.5 mm (diameter) -zirconia beads: 80% by volume; And carbon black and WAX were dispersed by treating with a beads mill (Ultra Visco Mill, manufactured by Aymex Co.) under the condition of Pass number: 3. Furthermore, 846 parts of 65% ethyl acetate solutions of [Low Molecular Weight Polyester 1] were added thereto, and the resulting mixture was treated once with a bead mill under the same conditions to obtain [Pigment-WAX Dispersion 7].

The concentration of the solid content of [Pigment / WAX Dispersion 7] was adjusted by evaporation of ethyl acetate, and then concentrated so that the solid content was 53% (measured after drying at 130 ° C. for 30 minutes). Got.

<Production of Toner Matrix Particles 7>

The following emulsification, desolvation, washing and drying steps were carried out to obtain parent particles.

<< oil painting >>

[Pigment and WAX dispersion 7] (780 parts), 120 parts of [Prepolymer 1] and 5 parts of [Ketamine Compound 1] were placed in a container. The resulting mixture was mixed together for 1 minute at 6,000 rpm with a TK homomixer (PRIMIX Corporation). Subsequently, 1,300 parts of [water phase 1] were added to the vessel, and then mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsified slurry 7].

<< desolventization >>

[Emulsification slurry 7] was added to a vessel equipped with a stirrer and a thermometer, and then desolvated at 30 ° C. for 10 hours, and aged at 45 ° C. for 5 hours to obtain [Dispersion Slurry 7].

<< cleaning and drying >>

[Dispersion slurry 7] (100 parts) was filtered under reduced pressure, followed by two series of treatments (1) to (4) described below to obtain [filtration cake 7]:

(1): Ion-exchanged water (100 parts) was added to the filter cake, and then mixed with a TK homomixer (10 minutes at 12,000 rpm), followed by filtration;

(2): 10% aqueous sodium hydroxide solution (100 parts) was added to the filter cake obtained in (1), and then mixed with a TK homomixer (30 minutes at 12,000 rpm), followed by filtration under reduced pressure;

(3): 10% hydrochloric acid (100 parts) was added to the filter cake obtained in (2), followed by mixing with a TK homomixer (10 minutes at 12,000 rpm), followed by filtration;

(4): Ion-exchanged water (300 parts) was added to the filter cake obtained in (3), and then mixed with a TK homomixer (10 minutes at 12,000 rpm), followed by filtration.

[Filtration cake 7] was dried for 48 hours at 45 ° C. with a pure air dryer, and then passed through a sieve having a mesh size of 75 μm to prepare [parent particles].

The parent particles were found to have a volume average particle diameter (Dv) of 5.01 μm and a ratio of volume average particle diameter (Dv) to number average particle diameter (Dn) (Dv / Dn) of 1.14.

The obtained mother particles (100 parts) were mixed with hydrophobic silica (0.7 parts) and hydrophobic titanium oxide (0.3 parts) using HENSCHEL MIXER to prepare a toner (toner of Example 7).

In addition, Table 4 below summarizes the particle diameter of the wax dispersion, the volume average particle diameter of the parent particles, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the parent particles.

(Example 8)

Preparation of Toner of Example 8

By repeating the procedure of Example 1 to prepare a wax dispersion except for changing the combination and mixing ratio of the synthetic ester waxes as shown in Tables 3-1 and 3-2 below while keeping the total amount of release agent unchanged. , Mother particles of Example 8 were prepared.

The parent particle (100 parts) of Example 8 obtained above was mixed with hydrophobic silica (0.7 parts) and hydrophobic titanium oxide (0.3 parts) using HENSCHEL MIXER to prepare a toner (toner of Example 8).

Table 4 below summarizes the particle diameter of the wax dispersion, the volume average particle diameter of the parent particles, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the parent particles.

(Example 9)

Preparation of Toner of Example 9

Preparation of Wax Dispersion 9

A vessel equipped with a stirring rod and a thermometer was prepared using 400 parts of [low molecular weight polyester 1], synthetic ester waxes (mixtures) as shown in Tables 3-1 and 3-2 below [ie, synthetic ester waxes (1) and ( 10 parts by mass of the mixture of 2) having a mass ratio (1) / (2) of 50/50] and 1,000 parts of ethyl acetate. The resulting mixture was then heated to 80 ° C. under stirring, held at 80 ° C. for 8 hours, and cooled to 24 ° C. for 1 hour. The obtained dispersion was fed at a feed rate of 1 kg / hour; Disk circumferential speed: 6 m / sec; Amount of injected 0.5 mm (diameter) -zirconia beads: 80% by volume; And a number of passes: 3, and treated with a bead mill (Ultra Visco Mill, manufactured by Aymex Co.) to disperse the synthetic ester wax (WAX) to obtain [Wax Dispersion 9].

[Wax Dispersion 9] was measured for the dispersion diameter using LA-920, and [Wax Dispersion 9] was found to have an average particle diameter (wax dispersion particle diameter) of 0.13 mu m.

<Production of Toner Matrix Particles 9>

A parent particle was prepared by repeating the procedure of Example 7 except that [Wax Dispersion 7] was changed to [Wax Dispersion 9].

The obtained parent particles were found to have a volume average particle diameter (Dv) of 5.25 µm and a ratio (Dv / Dn) of volume average particle diameter (Dv) to number average particle diameter (Dn) of 1.15.

The obtained mother particles (100 parts) were mixed with hydrophobic silica (0.7 parts) and hydrophobic titanium oxide (0.3 parts) using HENSCHEL MIXER to prepare a toner (toner of Example 9).

Table 4 below shows the particle size of the wax dispersion in the same manner as in Example 1; Volume average particle diameter of the parent particle; And the results obtained by measuring the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the parent particles.

(Example 10)

Preparation of Toner of Example 10

Preparation of Wax Dispersion 10

A vessel equipped with a stirring rod and a thermometer was prepared from 200 parts of [low molecular weight polyester 1], synthetic ester waxes (mixtures) as shown in Tables 3-1 and 3-2 below [ie, synthetic ester waxes (1) and ( Mixture of mass ratio (1) / (2) of 2) of 50/50] and 1,000 parts of ethyl acetate. The resulting mixture was then heated to 80 ° C. under stirring, held at 80 ° C. for 8 hours, and cooled to 24 ° C. for 1 hour. The obtained dispersion was fed at a feed rate of 1 kg / hour; Disk circumferential speed: 6 m / sec; Amount of injected 0.5 mm (diameter) -zirconia beads: 80% by volume; And a number of passes: 3, and treated with a beads mill (Ultra Visco Mill, manufactured by Aymex Co.) to disperse the synthetic ester wax (WAX) to obtain [Wax Dispersion 10].

[Wax Dispersion 10] was measured for the dispersion diameter using LA-920, and [Wax Dispersion 10] was found to have an average particle diameter (wax dispersion particle diameter) of 0.16 mu m.

<Production of Toner Matrix Particles 10>

A parent particle was prepared by repeating the procedure of Example 7 except that [Wax Dispersion 7] was changed to [Wax Dispersion 10].

The obtained mother particles were found to have a volume average particle diameter (Dv) of 5.18 mu m and a ratio (Dv / Dn) of volume average particle diameter (Dv) to number average particle diameter (Dn) of 1.14.

The obtained mother particle (100 parts) was mixed with hydrophobic silica (0.7 parts) and hydrophobic titanium oxide (0.3 parts) using HENSCHEL MIXER to prepare a toner (toner of Example 10).

Table 4 below shows the particle size of the wax dispersion in the same manner as in Example 1; Volume average particle diameter of the parent particle; And the results obtained by measuring the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the parent particles.

(Example 11)

Preparation of Toner of Example 11

<Production of Wax Dispersion 11>

A vessel equipped with a stirring rod and a thermometer was prepared from 400 parts of [low molecular weight polyester 1], synthetic ester waxes (mixtures) as shown in Tables 3-1 and 3-2 below [ie, synthetic ester waxes (1) and ( 35 parts of the mass ratio (1) / (2) of 2) to 50/50] and 1,000 parts of ethyl acetate. The resulting mixture was then heated to 80 ° C. under stirring, held at 80 ° C. for 8 hours, and cooled to 24 ° C. for 1 hour. The obtained dispersion was fed at a feed rate of 1 kg / hour; Disk circumferential speed: 6 m / sec; Amount of injected 0.5 mm (diameter) -zirconia beads: 80% by volume; And a number of passes: 3, and treated with a beads mill (Ultra Visco Mill, manufactured by Aymex Co.) to disperse the synthetic ester wax (WAX) to obtain [Wax Dispersion 11].

[Wax Dispersion 11] was measured for the dispersion diameter using LA-920, and [Wax Dispersion 11] was found to have an average particle diameter (wax dispersion particle diameter) of 0.18 mu m.

<Production of Toner Matrix Particles 11>

A parent particle was prepared by repeating the procedure of Example 7 except that [Wax Dispersion 7] was changed to [Wax Dispersion 11].

The obtained mother particles were found to have a volume average particle diameter (Dv) of 5.22 µm and a ratio (Dv / Dn) of volume average particle diameter (Dv) to number average particle diameter (Dn) of 1.13.

The obtained mother particle (100 parts) was mixed with hydrophobic silica (0.7 parts) and hydrophobic titanium oxide (0.3 parts) using HENSCHEL MIXER to prepare a toner (toner of Example 11).

Table 4 below shows the particle size of the wax dispersion in the same manner as in Example 1; Volume average particle diameter of the parent particle; And the results obtained by measuring the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the parent particles.

(Example 12 and Comparative Example 6)

By repeating the procedure of Example 1 to prepare a wax dispersion, except that the combination of synthetic ester waxes was changed as shown in Tables 3-1 and 3-2 below while keeping the total amount of release agent unchanged, Parent particles were prepared.

Table 4 below summarizes the results obtained by measuring the particle size and particle size distribution of the toner base particles in the same manner as in Example 1.

The obtained mother particles are mixed with the inorganic fine particles in the same manner as in Example 1 to prepare a toner.

(Example 13)

The toner was manufactured by repeating the procedure of Example 1 except that [Low Molecular Weight Polyester 1] was changed to [Low Molecular Weight Polyester 2].

(Comparative Example 7)

The toner was prepared by repeating the procedure of Example 1 except that [Low Molecular Weight Polyester 1], [Prepolymer 1], and [Ketamine Compound 1] were changed to [Styrene Acrylic Resin 1].

(Example 14)

Preparation of Wax Dispersion 14

A vessel equipped with a stirring rod and a thermometer was placed in 400 parts of [low molecular weight polyester 1], a synthetic ester wax (mixture) as shown in Tables 3-1 and 3-2 below [i.e., a synthetic ester wax (1), ( 2), (3), (4) and (5) mass ratio (1) / (2) / (3) / (4) / (5) is 50/13/13/13/11] 115 parts And 1,000 parts of ethyl acetate. The resulting mixture was then heated to 80 ° C. under stirring, held at 80 ° C. for 8 hours, and cooled to 24 ° C. for 1 hour. The obtained dispersion was fed at a feed rate of 1 kg / hour; Disk circumferential speed: 6 m / sec; Amount of injected 0.5 mm (diameter) -zirconia beads: 80% by volume; And a number of passes: 3, and treated with a beads mill (Ultra Visco Mill, manufactured by Aymex Co.) to disperse the synthetic ester wax (WAX) to obtain [Wax Dispersion Liquid 14].

[Wax Dispersion 14] was measured for the dispersion diameter using LA-920, and [Wax Dispersion 14] was found to have an average particle diameter (wax dispersion particle diameter) of 0.22 mu m.

<Production of Toner Matrix Particles 14>

A parent particle was prepared by repeating the procedure of Example 1 except that [Wax Dispersion 1] was changed to [Wax Dispersion 14].

The obtained parent particles were found to have a volume average particle diameter (Dv) of 5.05 μm and a ratio (Dv / Dn) of volume average particle diameter (Dv) to number average particle diameter (Dn) of 1.10.

The obtained mother particle (100 parts) was mixed with hydrophobic silica (0.7 parts) and hydrophobic titanium oxide (0.3 parts) using HENSCHEL MIXER to prepare a toner (toner of Example 14).

Table 4 below shows the particle size of the wax dispersion in the same manner as in Example 1; Volume average particle diameter of the parent particle; And the results obtained by measuring the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the parent particles.

Tables 3-1 and 3-2 show the amounts and types of materials used in Examples 1-14 and Comparative Examples 1-7, ie the combination and mixing ratio of the waxes; The amount (mass%) of component (N1) contained in the synthetic ester wax in the largest amount and the number of carbon atoms thereof; The amount (mass%) of component (N2) and the number of carbon atoms thereof contained in the synthetic ester wax in the second largest amount or in the same amount as component (N1); The amount of release agent (mass%) relative to the total amount of the parent particles; Presence or absence of crystalline polyester and amount of crystalline polyester relative to the release agent (mass%); And the kind of resin used is shown. In addition, the unit "mass%" in component N1 or N2 is "mass%" with respect to a mold release agent in a toner.

Table 4 sets forth the dispersion particle diameter of the wax dispersion, the volume average particle diameter (Dv) of the toner, and the Dv / Dn ratio (where Dn represents the number average particle diameter) in Examples 1 to 14 and Comparative Examples 1 to 7. .

Table 3-1

Table 3-2

[Table 4]

Each of the toners prepared in Examples 1 to 14 and Comparative Examples 1 to 7 was used to prepare a two-component developer, and the prepared two-component developer was evaluated. The carrier used for a two-component developer was manufactured by the following method.

[Manufacture of Carrier]

In the following, specific production examples of the carrier used for evaluation of the toner in the actual apparatus will be described. However, carriers usable in the present invention are not limited thereto.

<Composition of carrier>

Acrylic resin solution (HITALOID3001, product of Hitachi Chemical Co., Ltd., solid content: 50%): 21.0 parts

Guanamine solution (MYCOAT106, manufactured by Mitsui Scitech, solid content: 70%): 6.4 parts

Alumina particles [particle diameter: 0.3 μm, specific resistance: 10 ¹⁴ (Ω · cm)]: 7.6 parts

Silicone resin solution [solid content: 23% (SR2410, product of Dow Corning Toray Silicone Co., Ltd.)]: 65.0 parts

Amino silane [solid content: 100% (SH6020, manufactured by Dow Corning Toray Silicone Co., Ltd.)]: 1.0 parts

Toluene: 60 parts

Butyl Cellosolve: 60 parts

The carrier material is dispersed for 10 minutes with a homomixer at the above ratio to prepare a solution for forming a coating film of an acrylic resin and a silicone resin containing alumina particles. The coating film-forming solution prepared above had an average thickness of 0.15 on fired ferrite powder [(MgO) _1.8 (MnO) _49.5 (Fe ₂ O ₃ ) _48.0 , average particle diameter: 25 μm, serving as a core. It was applied using a Spira coater (manufactured by Okada Seiko Co.) to a 占 퐉 and then dried to obtain a coated ferrite powder. The obtained coated ferrite powder was calcined at 150 ° C. for 1 hour in an electric furnace. After cooling, the bulk of the ferrite powder was treated with a sieve having a mesh size of 106 μm to prepare carrier particles. Since the coating film covering the carrier surface can be observed by observing the cross section of the carrier particle under a transmission electron microscope, the average thickness of the coating film was measured through this observation. In this way, a carrier A having a weight average particle diameter of 35 µm was obtained.

[Production of Two-Component Developer]

The carrier A (100 parts) and each of the toners (7 parts) of Examples 1 to 14 and Comparative Examples 1 to 7 were uniformly mixed and charged together in a tubular mixer in which the container was rotated and stirred, A two-component developer was prepared.

[Evaluation of toner]

Each of the prepared two-component developers was evaluated in the following manner. The evaluation results are shown in Table 5 below.

<Evaluation conditions>

A device was obtained by modifying the IMAGIO MP C6000 (manufactured by Ricoh Company Ltd.) so that its anchorages could be driven independently and temperature controlled. Separately, plain paper sheets were provided each having an unfixed image formed at a toner deposition amount of 0.6 mg / cm ² . Then, the plain paper sheet was passed through the apparatus for fixing the toner on the paper sheet while gradually increasing the temperature of the fixing belt in contact with the medium, such as the paper.

[Lowest settling temperature]

The lowest temperature at which the fixed image does not adhere sufficiently on the paper sheet, and the phenomenon in which the unfixed toner is conveyed with the belt and adhered on the paper sheet in the second circulation to form an abnormal image does not occur. The minimum fixing temperature was defined as.

Maximum Settling Temperature

At the highest temperature (high temperature without offset), the fused image is excessively melted on the sheet of paper, and the melted toner is conveyed with the belt and adhered on the sheet of paper in the second circulation to form an abnormal image. The highest fixation temperature was defined.

[Settling Temperature Range]

The fixing temperature range was defined as the difference between the highest and lowest fixing temperatures.

Note that the difference between the highest and lowest fixing temperatures is preferably at least 40 ° C.

[Gloss of Glossy with Temperature]

When the release agent functions effectively, the gloss of the image increases with increasing fixing temperature. If the difference between the image gloss at high fusing temperature and that at low fusing temperature is small, this suggests that the release agent does not function sufficiently at high fusing temperature, making it difficult for the toner to be ejected from the fusing belt (ie, poor mold release). do. Thus, the difference between the image gloss at the highest fusing temperature minus 20 ° C. and the image gloss at the highest fusing temperature shows that the release agent functions effectively at high temperatures.

Therefore, after measuring the gloss A of the image fixed at [maximum fixing temperature-20 ° C.] and the gloss B of the image fixed at [maximum fixing temperature], the difference (B-A) between them was evaluated. .

It is preferable that the difference (B-A) of glossiness is 20 or more.

[Measuring of gloss]

In the evaluation of the change in gloss, gloss was measured at an incidence angle of 60 ° with a glossmeter (product of NIPPON DENSHOKU INDUSTRIES CO., LTD.). Note that the transfer sheet used was Type 6000-70W (Ricoh Company Ltd.). The higher the gloss measured, the higher the gloss of the image. In order to obtain a clear image with high color reproducibility, high gloss is preferable.

[Transfer efficiency (%)]

Running test outputting an A4 solid image with a toner deposition amount of 0.6 mg / cm ² as a test image using an evaluation machine obtained by modifying IMAGIO MP C6000 (manufactured by Ricoh Company Ltd.) with adjustable linear speed and transfer time. Was carried out with each developer. After outputting 10,000 or 100,000 test images, the transfer efficiency in secondary transfer was calculated using the following equation (1). Note that the evaluation criteria are as follows.

Secondary transfer efficiency (%) = [(amount of toner transferred on intermediate transfer medium minus the amount of toner remaining on intermediate transfer medium after secondary transfer) / amount of toner transferred on intermediate transfer medium] × 100 … (One)

The evaluation criteria are as follows.

A: 90% ≤ secondary transfer efficiency

B: 85% ≤ secondary transfer efficiency <90%

C: 80% ≤ secondary transfer efficiency <85%

D: secondary transfer efficiency <80%

[Contamination in the device]

After outputting 100,000 test images with IMAGIO MP C6000 (manufactured by Ricoh Company Ltd.), the amount of volatile components attached to the lid on the fixing belt member was visually judged. In a further running process, the volatile components melt and fall during operation of the device to contaminate the burn.

The evaluation criteria are as follows.

A: Almost no adhesion of contaminant components was observed.

B: The contaminant adhered to the extent that it can be observed visually.

C: adhesion of contaminants could be clearly observed; Contaminant was deposited to the extent that it immediately deposited and contaminated the burn.

D: The contaminating component adhered to such an extent that it would melt and fall and contaminate the image.

[Table 5]

From the above-mentioned evaluation results, it was confirmed that the toner of the present invention has a low fixing temperature, which saves energy, has a wide fixing temperature range, and is resistant to changes in the fixing temperature of the apparatus. In addition, the toner of the present invention does not involve contamination on the charged members such as the carrier and the charged blade, does not degrade the transferability over time, shows good print quality in the initial state, and stabilizes high image quality in continuous output. It could be confirmed that obtained. In addition, less contamination in the device due to the release agent was observed.

That is, the present invention provides an image forming toner, a developer, a developer accommodating container (toner container), and an image forming method for developing an electrostatic latent image on an image carrier in, for example, an electrophotographic apparatus and an electrophotographic recording apparatus. can do. They suppress contamination to images and contamination in the apparatus even in continuous use, and realize high quality image formation.

1: image carrier
2: charged member
3: developing device
4: toner
5: developing sleeve
6: transfer conveying belt
6a: bias roller
7: cleaning blade
8: recovery spring
9: recovery coil
10: Image Carrier and Cleaning Unit (PCU)
13: bounce screw
14: paddle (stirrer)
16: Reflection density detection sensor (P sensor)
17: toner density sensor
18: registration roller
20: static eliminator
S: Transfer Paper Sheet
r: image light

Claims (10)

Binding resin having an ester bond, and
Release agent
As a toner comprising:
The release agent comprises a first C30-C50 alkyl monoester compound and a second C30-C50 alkyl monoester compound,
The number of carbon atoms of the first C30-C50 alkyl monoester compound is different from the number of carbon atoms of the second C30-C50 alkyl monoester compound,
The amount of the first C30-C50 alkyl monoester compound is the highest among the release agents and the amount of the second C30-C50 alkyl monoester compound is the second highest among the release agents or the same as the amount of the first C30-C50 alkyl monoester compounds,
The amount of the first C30-C50 alkyl monoester compound is 30% by mass or more and less than 50% by mass with respect to the release agent,
The amount of the second C30-C50 alkyl monoester compound is 10% by mass or more and less than 50% by mass with respect to the release agent. The toner according to claim 1, wherein a difference between the number of carbon atoms of the first C30-C50 alkyl monoester compound and the number of carbon atoms of the second C30-C50 alkyl monoester compound is 1-12 in absolute value. The toner according to claim 1 or 2, wherein the total amount of the first C30-C50 alkyl monoester compound and the second C30-C50 alkyl monoester compound is 90% by mass or more based on the release agent. The release agent according to any one of claims 1 to 3, wherein the release agent further comprises a third C30-C50 alkyl monoester compound, the amount being the third highest of the release agents or the second C30-C50 alkyl monoester compound. A toner, wherein the total amount of the first C30-C50 alkyl monoester compound, the second C30-C50 alkyl monoester compound, and the third C30-C50 alkyl monoester compound is equal to or greater than 95% by mass relative to the release agent. The toner according to any one of claims 1 to 4, wherein the toner comprises the mother particles each containing a binder resin and a release agent, wherein the mother particles have a volume average particle diameter (Dv) of 3.0 µm or more and less than 6.0 µm. The toner according to any one of claims 1 to 5, wherein the amount of the releasing agent is 1% by mass to 20% by mass with respect to the parent particles. The toner according to any one of claims 1 to 6, wherein the binder resin having an ester bond contains a modified polyester. The toner according to any one of claims 1 to 7, wherein the binder resin having an ester bond contains crystalline polyester. Dissolving or dispersing at least one of a release agent and a binder resin having an ester bond and a binder resin precursor having an ester bond in an organic solvent to prepare a toner material liquid,
Emulsifying or dispersing the toner material liquid in an aqueous medium to prepare an emulsion or dispersion; and
Removing the organic solvent from the emulsion or dispersion to form parent particles
A method of manufacturing a toner according to any one of claims 1 to 8, comprising a. Charging the surface of the image carrier,
Exposing the surface of the charged image bearing to form an electrostatic latent image on the image bearing,
Developing a latent electrostatic image formed on the image carrier with a developer containing toner to form a toner image on the image carrier;
Transferring the toner image onto a recording medium, and
Fixing the transferred toner image onto a recording medium
A method for forming an image,
The image forming method according to any one of claims 1 to 8, wherein the toner is a toner according to any one of claims 1 to 8.

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